Patent Grant
11945985
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
In recent years, organic light emitting diodes (OLEDs) have attracted great attention from both academic and industrial areas due to their outstanding merits, like high color quality, wide-viewing angle, low cost fabrication, low power consumption, fast respond speed and high electron to photon conversion efficiency. Most of the organic light emitting diodes (OLEDs) are phosphorescent OLEDs using Iridium (Ir), palladium (Pd) and platinum (Pt) complexes, as these metal complexes have strong Spin-Orbital Coupling, they can efficiently emit light from their triplet exited state and reach nearly 100% internal efficiency.
There remains a need in the art for efficient and stable OLED components. This invention addresses this unmet need.
In one aspect, the present disclosure relates to a of General Formula I;
wherein:
In one embodiment, an organic light emitting diode (OLED) including the compound is provided. According to another embodiment, a light emitting device comprising the light emitting diode is provided.
The following detailed description of preferred embodiments of the disclosure will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities of the embodiments shown in the drawings.
The present disclosure relates in part to the unexpected discovery that increased conjugation increases MADF efficiency.
Definitions
It is to be understood that the figures and descriptions in the present disclosure have been simplified to illustrate elements that are relevant for a clear understanding of the present invention, while eliminating, for the purpose of clarity, many other elements found in the art related to phosphorescent organic light emitting devices and the like. Those of ordinary skill in the art may recognize that other elements and/or steps are desirable and/or required in implementing the disclosed embodiments. However, because such elements and steps are well known in the art, and because they do not facilitate a better understanding of the present disclosure, a discussion of such elements and steps is not provided herein. The disclosure herein is directed to all such variations and modifications to such elements and methods known to those skilled in the art.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods, materials and components similar or equivalent to those described herein can be used in the practice or testing of the disclosed embodiments, the preferred methods, and materials are described.
As used herein, each of the following terms has the meaning associated with it in this section.
The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element.
“About” as used herein when referring to a measurable value such as an amount, a temporal duration, and the like, is meant to encompass variations of 20%, ±10%, ±5%, +1%, or +0.1% from the specified value, as such variations are appropriate.
Throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, 6 and any whole and partial increments therebetween. This applies regardless of the breadth of the range.
Disclosed are the components to be used to prepare the compositions of the disclosure as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods of the invention.
As referred to herein, a linking atom or a linking group can connect two groups such as, for example, an N and C group. The linking atom can optionally, if valency permits, have other chemical moieties attached. For example, in one aspect, an oxygen would not have any other chemical groups attached as the valency is satisfied once it is bonded to two groups (e.g., N and/or C groups). In another aspect, when carbon is the linking atom, two additional chemical moieties can be attached to the carbon. Suitable chemical moieties include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, ═O, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.
The term “cyclic structure” or the like terms used herein refer to any cyclic chemical structure which includes, but is not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, and heterocyclyl.
As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this disclosure, the heteroatoms, such as nitrogen, can have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. This disclosure is not intended to be limited in any manner by the permissible substituents of organic compounds. Also, the terms “substitution” or “substituted with” include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. It is also contemplated that, in certain aspects, unless expressly indicated to the contrary, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).
The term “alkyl” as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol, as described herein. A “lower alkyl” group is an alkyl group containing from one to six (e.g., from one to four) carbon atoms.
Throughout the specification “alkyl” is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group. For example, the term “halogenated alkyl” or “haloalkyl” specifically refers to an alkyl group that is substituted with one or more halide, e.g., fluorine, chlorine, bromine, or iodine. The term “alkoxyalkyl” specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below. The term “alkylamino” specifically refers to an alkyl group that is substituted with one or more amino groups, as described below, and the like. When “alkyl” is used in one instance and a specific term such as “alkylalcohol” is used in another, it is not meant to imply that the term “alkyl” does not also refer to specific terms such as “alkylalcohol” and the like.
This practice is also used for other groups described herein. That is, while a term such as “cycloalkyl” refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moieties can, in addition, be specifically identified herein; for example, a particular substituted cycloalkyl can be referred to as, e.g., an “alkylcycloalkyl.” Similarly, a substituted alkoxy can be specifically referred to as, e.g., a “halogenated alkoxy,” a particular substituted alkenyl can be, e.g., an “alkenylalcohol,” and the like. Again, the practice of using a general term, such as “cycloalkyl,” and a specific term, such as “alkylcycloalkyl,” is not meant to imply that the general term does not also include the specific term.
The term “cycloalkyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and the like. The term “heterocycloalkyl” is a type of cycloalkyl group as defined above, and is included within the meaning of the term “cycloalkyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl group and heterocycloalkyl group can be substituted or unsubstituted. The cycloalkyl group and heterocycloalkyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol as described herein.
The term “polyalkylene group” as used herein is a group having two or more CH2 groups linked to one another. The polyalkylene group can be represented by the formula —(CH2)a—, where “a” is an integer of from 2 to 500.
The terms “alkoxy” and “alkoxyl” as used herein to refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, an “alkoxy” group can be defined as -OA1 where A1 is alkyl or cycloalkyl as defined above. “Alkoxy” also includes polymers of alkoxy groups as just described; that is, an alkoxy can be a polyether such as -OA1-OA2 or -OA1-(OA2)a-OA3, where “a” is an integer of from 1 to 200 and A1, A2, and A3 are alkyl and/or cycloalkyl groups.
The term “alkenyl” as used herein is a hydrocarbon group of from 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (A1A2)C═C(A3A4) are intended to include both the E and Z isomers. This can be presumed in structural formulae herein wherein an asymmetric alkene is present, or it can be explicitly indicated by the bond symbol C═C. The alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.
The term “cycloalkenyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms and containing at least one carbon-carbon double bond, i.e., C═C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term “heterocycloalkenyl” is a type of cycloalkenyl group as defined above, and is included within the meaning of the term “cycloalkenyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl group and heterocycloalkenyl group can be substituted or unsubstituted. The cycloalkenyl group and heterocycloalkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.
The term “alkynyl” as used herein is a hydrocarbon group of 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon triple bond. The alkynyl group can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.
The term “cycloalkynyl” as used herein is a non-aromatic carbon-based ring composed of at least seven carbon atoms and containing at least one carbon-carbon triple bound. Examples of cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term “heterocycloalkynyl” is a type of cycloalkenyl group as defined above, and is included within the meaning of the term “cycloalkynyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkynyl group and heterocycloalkynyl group can be substituted or unsubstituted. The cycloalkynyl group and heterocycloalkynyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.
The term “aryl” as used herein is a group that contains any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term “aryl” also includes “heteroaryl,” which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term “non-heteroaryl,” which is also included in the term “aryl,” defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein. The term “biaryl” is a specific type of aryl group and is included in the definition of “aryl.” Biaryl refers to two aryl groups that are bound together via a fused ring structure, as in naphthalene, or are attached via one or more carbon-carbon bonds, as in biphenyl.
The term “aldehyde” as used herein is represented by the formula —C(O)H. Throughout this specification “C(O)” is a short hand notation for a carbonyl group, i.e., C═O.
The terms “amine” or “amino” as used herein are represented by the formula —NA1A2, where A1 and A2 can be, independently, hydrogen or alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term “alkylamino” as used herein is represented by the formula —NH(-alkyl) where alkyl is a described herein. Representative examples include, but are not limited to, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, (sec-butyl)amino group, (tert-butyl)amino group, pentylamino group, isopentylamino group, (tert-pentyl)amino group, hexylamino group, and the like.
The term “dialkylamino” as used herein is represented by the formula —N(-alkyl)2 where alkyl is a described herein. Representative examples include, but are not limited to, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, di(sec-butyl)amino group, di(tert-butyl)amino group, dipentylamino group, diisopentylamino group, di(tert-pentyl)amino group, dihexylamino group, N-ethyl-N-methylamino group, N-methyl-N-propylamino group, N-ethyl-N-propylamino group and the like.
The term “carboxylic acid” as used herein is represented by the formula —C(O)OH.
The term “ester” as used herein is represented by the formula —OC(O)A1 or —C(O)OA1, where A1 can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term “polyester” as used herein is represented by the formula -(A1O(O)C-A2-C(O)O), or -(A1O(O)C-A2-OC(O))a—, where A1 and A2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and “a” is an integer from 1 to 500. “Polyester” is as the term used to describe a group that is produced by the reaction between a compound having at least two carboxylic acid groups with a compound having at least two hydroxyl groups.
The term “ether” as used herein is represented by the formula A1OA2, where A1 and A2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein. The term “polyether” as used herein is represented by the formula -(A1O-A2O)a—, where A1 and A2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and “a” is an integer of from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.
The term “halide” as used herein refers to the halogens fluorine, chlorine, bromine, and iodine.
The term “heterocyclyl,” as used herein refers to single and multi-cyclic non-aromatic ring systems and “heteroaryl” as used herein refers to single and multi-cyclic aromatic ring systems: in which at least one of the ring members is other than carbon. The term “heterocyclyl” includes azetidine, dioxane, furan, imidazole, isothiazole, isoxazole, morpholine, oxazole, oxazole, including, 1,2,3-oxadiazole, 1,2,5-oxadiazole and 1,3,4-oxadiazole, piperazine, piperidine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, tetrahydrofuran, tetrahydropyran, tetrazine, including 1,2,4,5-tetrazine, tetrazole, including 1,2,3,4-tetrazole and 1,2,4,5-tetrazole, thiadiazole, including, 1,2,3-thiadiazole, 1,2,5-thiadiazole, and 1,3,4-thiadiazole, thiazole, thiophene, triazine, including 1,3,5-triazine and 1,2,4-triazine, triazole, including, 1,2,3-triazole, 1,3,4-triazole, and the like.
The term “hydroxyl” as used herein is represented by the formula —OH.
The term “ketone” as used herein is represented by the formula A1C(O)A2, where A1 and A2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term “azide” as used herein is represented by the formula —N3.
The term “nitro” as used herein is represented by the formula —NO2.
The term “nitrile” as used herein is represented by the formula —CN.
The term “ureido” as used herein refers to a urea group of the formula —NHC(O)NH2 or —NHC(O)NH—.
The term “phosphoramide” as used herein refers to a group of the formula —P(O)(NA1A2)2, where A1 and A2 can be, independently, hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term “carbamoyl” as used herein refers to an amide group of the formula —CONA1A2, where A1 and A2 can be, independently, hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term “sulfamoyl” as used herein refers to a group of the formula —S(O)2NA1A2, where A1 and A2 can be, independently, hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term “silyl” as used herein is represented by the formula —SiA1A2A3, where A1, A2, and A3 can be, independently, hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term “sulfo-oxo” as used herein is represented by the formulas —S(O)Al, —S(O)2A1, —OS(O)2A1, or —OS(O)2OA1, where A1 is hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout this specification “S(O)” is a short hand notation for S═O. The term “sulfonyl” is used herein to refer to the sulfo-oxo group represented by the formula —S(O)2A1, where Al is hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term “sulfone” as used herein is represented by the formula A'S(O)2A2, where A1 and A2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term “sulfoxide” as used herein is represented by the formula A'S(O)A2, where Aland A2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term “thiol” as used herein is represented by the formula —SH.
The term “polymeric” includes polyalkylene, polyether, polyester, and other groups with repeating units, such as, but not limited to —(CH2O)n—CH3, —(CH2CH2O)n—CH3, —[CH2CH(CH3)]n—CH3, —[CH2CH(COOCH3)]n—CH3, —[CH2CH(COOCH2CH3)]n—CH3, and —[CH2CH(COOtBu)]n—CH3, where n is an integer (e.g., n>1 or n>2).
“R,” “R1,” “R2,” “R3,” “Rn,” where n is an integer, as used herein can, independently, include hydrogen or one or more of the groups listed above. For example, if R1 is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can optionally be substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halide, and the like. Depending upon the groups that are selected, a first group can be incorporated within a second group or, alternatively, the first group can be pendant (i.e., attached) to the second group. For example, with the phrase “an alkyl group comprising an amino group,” the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group.
As described herein, compounds of the disclosure may contain “optionally substituted” moieties. In general, the term “substituted,” whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned by this disclosure are preferably those that result in the formation of stable or chemically feasible compounds. It is also contemplated that, in certain aspects, unless expressly indicated to the contrary, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).
In some aspects, a structure of a compound can be represented by a formula:
which is understood to be equivalent to a formula:
wherein n is typically an integer. That is, Rn is understood to represent five independent substituents, Rn(a), Rn(b), Rn(c), Rn(d), Rn(e). By “independent substituents,” it is meant that each R substituent can be independently defined. For example, if in one instance Rn(a) is halogen, then Rn(b) is not necessarily halogen in that instance.
Several references to R, R1, R2, R3, R4, R5, R6, etc. are made in chemical structures and moieties disclosed and described herein. Any description of R, R1, R2, R3, R4, R5, R6, etc. in the specification is applicable to any structure or moiety reciting R, R1, R2, R3, R4, R5, R6, etc. respectively.
Compounds
The compounds disclosed herein are suited for use in a wide variety of optical and electro-optical devices, including, but not limited to, photo-absorbing devices such as solar- and photo-sensitive devices, organic light emitting devices (OLEDs), photo-emitting devices, or devices capable of both photo-absorption and emission and as markers for bio-applications.
The compounds disclosed herein are useful in a variety of applications. As light emitting materials, the compounds can be useful in organic light emitting devices (OLEDs), luminescent devices and displays, and other light emitting devices.
In another aspect, the compounds can provide improved efficiency, improved operational lifetimes, or both in lighting devices, such as, for example, organic light emitting devices, as compared to conventional materials.
The compounds of the disclosure can be made using a variety of methods, including, but not limited to those recited in the examples provided herein.
Compounds of the Invention
In one aspect, the present invention relates to a compound of General Formula I:
wherein:
In one embodiment, two additional adjacent groups R2 together are represented by Formula B:
In one embodiment, the compound is represented by General Formula II, General Formula III, General Formula IV, General Formula V, General Formula VI, or General Formula VII:
wherein:
In one embodiment, the compound is represented by General Formula VIII, General Formula IX, General Formula X, General Formula XI, General Formula XII, or General Formula XIII:
wherein:
In one embodiment, the compound is represented by General Formula XIV, General Formula XV, General Formula XVI, or General Formula XVII:
wherein:
In one embodiment, the compound is represented by General Formula XVIII, General Formula XIX, General Formula XX, or General Formula XXI.
wherein:
In one embodiment,
is represented by one of the following structures:
wherein:
In one embodiment,
is represented by one of the following structures:
wherein:
In one embodiment,
is represented by one of the following structures:
wherein:
In one embodiment, the compound is selected from following structures:
Compositions and Devices of the Invention
Also disclosed herein are organic emitting diodes or light emitting devices comprising one or more compound and/or compositions disclosed herein.
In one aspect, the device is an electro-optical device. Electro-optical devices include, but are not limited to, photo-absorbing devices such as solar- and photo-sensitive devices, organic light emitting devices, photo-emitting devices, or devices capable of both photo-absorption and emission and as markers for bio-applications. For example, the device can be an OLED.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art. Such devices are disclosed herein which comprise one or more of the compounds or compositions disclosed herein.
OLEDs can be produced by methods known to those skilled in the art. In general, the OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate. Suitable substrates include, for example, glass, inorganic materials such as ITO or IZO or polymer films. For the vapor deposition, customary techniques may be used, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others.
In an alternative process, the organic layers may be coated from solutions or dispersions in suitable solvents, in which case coating techniques known to those skilled in the art are employed. Suitable coating techniques are, for example, spin-coating, the casting method, the Langmuir-Blodgett (“LB”) method, the inkjet printing method, dip-coating, letterpress printing, screen printing, doctor blade printing, slit-coating, roller printing, reverse roller printing, offset lithography printing, flexographic printing, web printing, spray coating, coating by a brush or pad printing, and the like. Among the processes mentioned, in addition to the aforementioned vapor deposition, preference is given to spin-coating, the inkjet printing method and the casting method since they are particularly simple and inexpensive to perform. In the case that layers of the OLED are obtained by the spin-coating method, the casting method or the inkjet printing method, the coating can be obtained using a solution prepared by dissolving the composition in a concentration of 0.0001 to 90% by weight in a suitable organic solvent such as benzene, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethyl sulfoxide, water and mixtures thereof.
Compounds described herein can be used in a light emitting device such as an OLED.
In various aspects, any of the one or more layers depicted in
Light processing material 108 may include one or more compounds of the present disclosure optionally together with a host material. The host material can be any suitable host material known in the art. The emission color of an OLED is determined by the emission energy (optical energy gap) of the light processing material 108, which can be tuned by tuning the electronic structure of the emitting compounds, the host material, or both. Both the hole-transporting material in the HTL layer 106 and the electron-transporting material(s) in the ETL layer 110 may include any suitable hole-transporter known in the art.
Compounds described herein may exhibit phosphorescence. Phosphorescent OLEDs (i.e., OLEDs with phosphorescent emitters) typically have higher device efficiencies than other OLEDs, such as fluorescent OLEDs. Light emitting devices based on electrophosphorescent emitters are described in more detail in WO2000/070655 to Baldo et al., which is incorporated herein by this reference for its teaching of OLEDs, and in particular phosphorescent OLEDs.
As contemplated herein, an OLED of the present invention may include an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include a host and a phosphorescent dopant. The organic layer can include a compound of the invention and its variations as described herein.
In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
In one embodiment, the consumer product is selected from the group consisting of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, and a sign.
In some embodiments of the emissive region, the emissive region further comprises a host, wherein the host comprises at least one selected from the group consisting of metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
The organic layer can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the hosts used may be a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport. In some embodiments, the host can include a metal complex. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡C—CnH2n+1, Ar1, Ar1-Ar2, and CnH2n-Ar1, or the host has no substitutions. In the preceding substituents n can range from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host can be an inorganic compound. For example, a Zn containing inorganic material e.g. ZnS.
Suitable hosts may include, but are not limited to, mCP (1,3-bis(carbazol-9-yl)benzene), mCPy (2,6-bis(N-carbazolyl)pyridine), TCP (1,3,5-tris(carbazol-9-yl)benzene), TCTA (4,4′,4″-tris(carbazol-9-yl)triphenylamine), TPBi (1,3,5-tris(1-phenyl-1-H-benzimidazol-2-yl)benzene), mCBP (3,3-di(9H-carbazol-9-yl)biphenyl), pCBP (4,4′-bis(carbazol-9-yl)biphenyl), CDBP (4,4′-bis(9-carbazolyl)-2,2′-dimethylbiphenyl), DMFL-CBP (4,4′-bis(carbazol-9-yl)-9,9-dimethylfluorene), FL-4CBP (4,4′-bis(carbazol-9-yl)-9,9-bis(9-phenyl-9H-carbazole)fluorene), FL-2CBP (9,9-bis(4-carbazol-9-yl)phenyl)fluorene, also abbreviated as CPF), DPFL-CBP (4,4′-bis(carbazol-9-yl)-9,9-ditolylfluorene), FL-2CBP (9,9-bis(9-phenyl-9H-carbazole)fluorene), Spiro-CBP (2,2′,7,7′-tetrakis(carbazol-9-yl)-9,9′-spirobifluorene), ADN (9,10-di(naphth-2-yl)anthracene), TBADN (3-tert-butyl-9,10-di(naphth-2-yl)anthracene), DPVBi (4,4′-bis(2,2-diphenylethen-1-yl)-4,4′-dimethylphenyl), p-DMDPVBi (4,4′-bis(2,2-diphenylethen-1-yl)-4,4′-dimethylphenyl), TDAF (tert(9,9-diarylfluorene)), BSBF (2-(9,9′-spirobifluoren-2-yl)-9,9′-spirobifluorene), TSBF (2,7-bis(9,9′-spirobifluoren-2-yl)-9,9′-spirobifluorene), BDAF (bis(9,9-diarylfluorene)), p-TDPVBi (4,4′-bis(2,2-diphenylethen-1-yl)-4,4′-di-(tert-butyl)phenyl), TPB3 (1,3,5-tri(pyren-1-yl)benzene, PBD (2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole), BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), BP-OXD-Bpy (6,6′-bis[5-(biphenyl-4-yl)-1,3,4-oxadiazo-2-yl]-2,2′-bipyridyl), NTAZ (4-(naphth-1-yl)-3,5-diphenyl-4H-1,2,4-triazole), Bpy-OXD (1,3-bis[2-(2,2′-bipyrid-6-yl)-1,3,4oxadiazo-5-yl]benzene), BPhen (4,7-diphenyl-1,10-phenanthroline), TAZ (3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole), PADN (2-phenyl-9,10-di(naphth-2-yl)anthracene), Bpy-FOXD (2,7-bis[2-(2,2′-bipyrid-6-yl)-1,3,4-oxadiazol-5-yl]-9,9-dimethylfluorene), OXD-7 (1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazol-5-yl]benzene), HNBphen (2-(naphth-2-yl)-4,7-diphenyl-1,10-phenanthroline), NBphen (2,9-bis(naphth-2-yl)-4,7-diphenyl-1,10-phenanthroline), 3TPYMB (tris(2,4,6-trimethyl-3-(pyrid-3-yl)phenyl)borane), 2-NPIP (1-methyl-2-(4-(naphth-2-yl)phenyl)-1H-imidazo[4,5-f]-[1,10]phenanthroline), Liq (8-hydroxyquinolinolatolithium), and Alq (bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminum), and also of mixtures of the aforesaid substances.
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.
A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein.
The invention is further described in detail by reference to the following experimental examples. These examples are provided for purposes of illustration only, and are not intended to be limiting unless otherwise specified. Thus, the invention should in no way be construed as being limited to the following examples, but rather, should be construed to encompass any and all variations which become evident as a result of the teaching provided herein.
Without further description, it is believed that one of ordinary skill in the art can, using the preceding description and the following illustrative examples, make and utilize the composite materials of the present invention and practice the claimed methods. The following working examples therefore, specifically point out the preferred embodiments of the present invention, and are not to be construed as limiting in any way the remainder of the disclosure.
The metal-assisted delayed fluorescence (MADF) emission process is capable of harvesting all electrogenerated excitons. As illustrated in
Ligands designed under this protocol are focused on 8-base or 2-base ligands. The T1 energy level is kept relatively constant, while an expansion of conjugation lowers the S1 energy level (
In one embodiment, an exemplary compound may be prepared according to the following scheme. PL data for this compound is presented in
A0 (10 mmol, 1.0 eq), B0 (12 mmol, 1.2 eq), Pd(dppf)Cl2 (0.8 mmol, 0.08 eq), and K2CO3 (30 mmol, 3.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent THF/H2O (5/3, 80 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at reflux overnight and then cooled down to ambient temperature. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product C0 in 95% yield.
C0 (8 mmol, 1.0 eq), D0 (8 mmol, 1.0 eq), 45 mL of DMF and 5 mL of distilled water were added to a flask equipped with a magnetic stir bar. The mixture was stirred in an oil bath at 90° C. for 2 days and then cooled down to ambient temperature. 200 mL of distilled water was added in the mixture. Then the system was filtered and washed with ethyl acetate and acetone to obtain the desired product E0 in 86% yield.
E0 (1 mmol, 1.0 eq), Pd(OAc)2 (0.1 mmol, 0.1 eq), Xphos (0.2 mmol, 0.2 eq), K2CO3 (3 mmol, 3.0 eq), and 15 mL of DMF were added to a flask equipped with a magnetic stir bar. The flask was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. The mixture was stirred in an oil bath at 160° C. for 2 days and then cooled down to ambient temperature. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica using hexane/ethyl acetate as eluent to obtain the desired product F0 in 43% yield.
F0 (0.4 mmol, 1.0 eq), and 6 mL of HOAc and 2 mL of HBr were added to a flask equipped with a magnetic stir bar. The mixture was stirred in an oil bath at reflux for several; days and then cooled down to ambient temperature. The solvent was neutralized with K2CO3, and then filtered and washed with distilled water to obtain the desired product 7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol in 95% yield.
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-(3-bromophenyl)pyridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product 3O8-Cz56 in 70% yield.
3O8-Cz56 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product Pd3O8-Cz56 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-(3-bromophenyl)-4-(tert-butyl)pyridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L1 in 30%˜70% yield.
L1 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC1 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-(3-bromo-5-(tert-butyl)phenyl)-4-(tert-butyl)pyridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L2 in 30%˜70% yield.
L2 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC2 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 11-bromodibenzo[f,h]quinoline (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L3 in 30%˜70% yield.
L3 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC3 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-bromo-7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L4 in 30%˜70% yield.
L4 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC4 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
L4 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC5 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-bromo-9-(pyridin-2-yl)-9H-carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L6 in 30%˜70% yield.
L6 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC6 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L7 in 30%˜70% yield.
L7 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC7 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-bromo-6-(tert-butyl)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L8 in 30%˜70% yield.
L8 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC8 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 3-bromo-9,9-dimethyl-10-(pyridin-2-yl)-9,10-dihydroacridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L9 in 30%˜70% yield.
L9 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC9 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 3-bromo-10-(4-(tert-butyl)pyridin-2-yl)-9,9-dimethyl-9,10-dihydroacridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L10 in 30%˜70% yield.
L10 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC10 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 3-bromo-9,9-diphenyl-10-(pyridin-2-yl)-9,10-dihydroacridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L11 in 30%˜70% yield.
L11 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC11 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 3-bromo-10-(4-(tert-butyl)pyridin-2-yl)-9,9-diphenyl-9,10-dihydroacridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L12 in 30%˜70% yield.
L12 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC12 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 11-bromo-8,8-dimethyl-8H-pyrido[3′,2′:4,5]pyrrolo[3,2,1-de]acridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L13 in 30%˜70% yield.
L13 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC13 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 11-bromo-8,8-diphenyl-8H-pyrido[3′,2′:4,5]pyrrolo[3,2,1-de]acridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L14 in 30%˜70% yield.
L14 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC14 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 11-bromo-5,5-dimethyl-5H-[1,8]naphthyridino[3,2,1-jk]carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L15 in 30%˜70% yield.
L15 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC15 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-benzo[4,5]imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 11-bromo-5,5-diphenyl-5H-[1,8]naphthyridino[3,2,1-jk]carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L16 in 30%˜70% yield.
L16 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC16 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
5,20-diphenyl-5,20-dihydrobenzo[4,5]imidazo[1,2-f]diindolo[2,3-a:2′,3′-c]phenanthridin-8-ol (1 mmol, 1.0 eq), 2-(3-bromophenyl)pyridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L17 in 30%˜70% yield.
L17 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC17 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
5,20-diphenyl-5,20-dihydrobenzo[4,5]imidazo[1,2-f]diindolo[2,3-a:2′,3′-c]phenanthridin-8-ol (1 mmol, 1.0 eq), 8-bromo-5,20-diphenyl-5,20-dihydrobenzo[4,5]imidazo[1,2-f]diindolo[2,3-a:2′,3′-c]phenanthridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L18 in 30%˜70% yield.
L18 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC18 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
L18 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC19 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
5,20-diphenyl-5,20-dihydrobenzo[4,5]imidazo[1,2-f]diindolo[2,3-a:2′,3′-c]phenanthridin-8-ol (1 mmol, 1.0 eq), 11-bromodibenzo[f,h]quinoline (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L20 in 30%˜70% yield.
L20 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC20 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
5,20-diphenyl-5,20-dihydrobenzo[4,5]imidazo[1,2-f]diindolo[2,3-a:2′,3′-c]phenanthridin-8-ol (1 mmol, 1.0 eq), 2-bromo-9-(pyridin-2-yl)-9H-carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L21 in 30%˜70% yield.
L21 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC21 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
5,20-diphenyl-5,20-dihydrobenzo[4,5]imidazo[1,2-f]diindolo[2,3-a:2′,3′-c]phenanthridin-8-ol (1 mmol, 1.0 eq), 11-bromo-5,5-dimethyl-5H-[1,8]naphthyridino[3,2,1-jk]carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L22 in 30%˜70% yield.
L22 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC22 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
5,20-diphenyl-5,20-dihydrobenzo[4,5]imidazo[1,2-f]diindolo[2,3-a:2′,3′-c]phenanthridin-8-ol (1 mmol, 1.0 eq), 3-bromo-9,9-dimethyl-10-(pyridin-2-yl)-9,10-dihydroacridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L23 in 30%˜70% yield.
L23 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC23 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
5,20-diphenyl-5,20-dihydrobenzo[4,5]imidazo[1,2-f]diindolo[2,3-a:2′,3′-c]phenanthridin-8-ol (1 mmol, 1.0 eq), 11-bromo-8,8-dimethyl-8H-pyrido[3′,2′:4,5]pyrrolo[3,2,1-de]acridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L24 in 30%˜70% yield.
L24 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC24 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
13-phenyl-13H-imidazo[1,2-f]indolo[3,2-b]phenanthridin-5-ol (1 mmol, 1.0 eq), 2-(3-bromophenyl)pyridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L25 in 30%˜70% yield.
L25 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC25 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
L25 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC26 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
13-phenyl-13H-imidazo[1,2-f]indolo[3,2-b]phenanthridin-5-ol (1 mmol, 1.0 eq), 11-bromoimidazo[1,2-f]phenanthridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L27 in 30%˜70% yield.
L27 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC27 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
L27 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC28 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
13-phenyl-13H-imidazo[1,2-f]indolo[3,2-b]phenanthridin-5-ol (1 mmol, 1.0 eq), 5-bromo-13-phenyl-13H-imidazo[1,2-f]indolo[3,2-b]phenanthridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L29 in 30%˜70% yield.
L29 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC29 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
L29 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC30 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
13-phenyl-13H-imidazo[1,2-f]indolo[3,2-b]phenanthridin-5-ol (1 mmol, 1.0 eq), 2-bromo-9-(pyridin-2-yl)-9H-carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L31 in 30%˜70% yield.
L31 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC31 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
L31 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC32 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
13-phenyl-13H-imidazo[1,2-f]indolo[3,2-b]phenanthridin-5-ol (1 mmol, 1.0 eq), 11-bromo-5,5-dimethyl-5H-[1,8]naphthyridino[3,2,1-jk]carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L33 in 30%˜70% yield.
L33 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC34 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
L33 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC34 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
13-phenyl-13H-imidazo[1,2-f]indolo[3,2-b]phenanthridin-5-ol (1 mmol, 1.0 eq), 3-bromo-9,9-dimethyl-10-(pyridin-2-yl)-9,10-dihydroacridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L35 in 30%˜70% yield.
L35 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC35 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
L35 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC36 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
13-phenyl-13H-imidazo[1,2-f]indolo[3,2-b]phenanthridin-5-ol (1 mmol, 1.0 eq), 11-bromo-8,8-dimethyl-8H-pyrido[3′,2′:4,5]pyrrolo[3,2,1-de]acridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L37 in 30%˜70% yield.
L37 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC37 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
L37 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC38 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-(3-bromophenyl)pyridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L39 in 30%˜70% yield.
L39 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC39 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-bromo-9-(pyridin-2-yl)-9H-carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product ON2-Cz56 in 30%˜70% yield.
ON2-Cz56 (0.20 mmol, 1.0 eq), Pd(OAc)2 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product PdON2-CZ56 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme. The photoluminescence spectrum of this compound is presented in
ON2-CZ56 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product PtON2-CZ56 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
7-phenyl-7H-imidazo[1,2-f]indolo[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product ON2-Cz56-tbu in 30%˜70% yield.
ON2-Cz56-tbu (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product PtON2-CZ56-tbu in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
Benzo[4,5]imidazo[1,2-f]benzo[4,5]thieno[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-(3-bromophenyl)pyridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L40 in 56% yield.
L40 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC40 in 59% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
Benzo[4,5]imidazo[1,2-f]benzo[4,5]thieno[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-(3-bromophenyl)-4-(tert-butyl)pyridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L41 in 30%˜70% yield.
L41 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC41 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
Benzo[4,5]imidazo[1,2-f]benzo[4,5]thieno[2,3-c]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-bromobenzo[4,5]imidazo[1,2-f]benzo[4,5]thieno[2,3-c]phenanthridine (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L42 in 30%˜70% yield.
L42 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC42 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
L42 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC43 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
Benzo[4,5]thieno[2,3-c]imidazo[1,2-f]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-bromo-9-(pyridin-2-yl)-9H-carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product L44 in 30%˜70% yield.
L44 (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product MC44 in 10%˜50% yield.
In one embodiment, an exemplary compound may be prepared according to the following scheme:
Benzo[4,5]thieno[2,3-c]imidazo[1,2-f]phenanthridin-2-ol (1 mmol, 1.0 eq), 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.2 mmol, 1.2 eq), CuI (0.2 mmol, 0.2 eq), picolinic acid (0.4 mmol, 0.4 eq) and K3PO4 (2 mmol, 2.0 eq) were added to a dry Shlenck tube equipped with a magnetic stir bar. The tube was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated for a total of three times. Then solvent DMSO (10 mL) was added under the protection of nitrogen. The mixture was stirred in an oil bath at a temperature of 100° C. for 3 days and then cooled down to ambient temperature, diluted with ethyl acetate. The mixture was washed with water three times and then dried over sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate as eluent to obtain the desired product ON2-Sz56-tbu in 30%˜70% yield.
ON2-Sz56-tbu (0.20 mmol, 1.0 eq), K2PtCl4 (0.24 mmol, 1.2 eq) and n-Bu4NBr (0.02 mmol, 0.1 eq) were added to a dry three-necked flask. Then the flask underwent the procedure of the evacuation and backfill with nitrogen for three times. Solvent of HOAc (10 mL) was added under the protection of nitrogen. Then the mixture was stirred in an oil bath under reflux for 3 days, then cooled down to ambient temperature. Then the solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain to obtain the desired product PtON2-Sz56-tbu in 10%˜50% yield.
The disclosures of each and every patent, patent application, and publication cited herein are hereby incorporated herein by reference in their entirety. While this invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of this invention may be devised by others skilled in the art without departing from the true spirit and scope of the invention. The appended claims are intended to be construed to include all such embodiments and equivalent variations.
The present application claims priority to U.S. Provisional Application No. 63/026,806, filed May 19, 2020, which is incorporated by reference herein in its entirety.
This invention was made with government support under DE-EE0008721 awarded by the Department of Energy. The government has certain rights in the invention.
| Number | Name | Date | Kind |
|---|---|---|---|
| 4769292 | Tang | Sep 1988 | A |
| 5451674 | Silver | Sep 1995 | A |
| 5641878 | Dandliker | Jun 1997 | A |
| 5707745 | Forrest | Jan 1998 | A |
| 5844363 | Gu | Dec 1998 | A |
| 6200695 | Arai | Mar 2001 | B1 |
| 6303238 | Thompson | Oct 2001 | B1 |
| 6780528 | Tsuboyama | Aug 2004 | B2 |
| 7002013 | Chi | Feb 2006 | B1 |
| 7037599 | Culligan | May 2006 | B2 |
| 7064228 | Yu | Jun 2006 | B1 |
| 7268485 | Tyan | Sep 2007 | B2 |
| 7279704 | Walters | Oct 2007 | B2 |
| 7332232 | Ma | Feb 2008 | B2 |
| 7442797 | Itoh | Oct 2008 | B2 |
| 7501190 | Ise | Mar 2009 | B2 |
| 7635792 | Cella | Dec 2009 | B1 |
| 7655322 | Forrest | Feb 2010 | B2 |
| 7854513 | Quach | Dec 2010 | B2 |
| 7947383 | Ise | May 2011 | B2 |
| 8106199 | Jabbour | Jan 2012 | B2 |
| 8133597 | Yasukawa | Mar 2012 | B2 |
| 8389725 | Li | Mar 2013 | B2 |
| 8617723 | Stoessel | Dec 2013 | B2 |
| 8669364 | Li | Mar 2014 | B2 |
| 8778509 | Yasukawa | Jul 2014 | B2 |
| 8816080 | Li | Aug 2014 | B2 |
| 8846940 | Li | Sep 2014 | B2 |
| 8871361 | Xia | Oct 2014 | B2 |
| 8927713 | Li | Jan 2015 | B2 |
| 8933622 | Kawami | Jan 2015 | B2 |
| 8946417 | Jian | Feb 2015 | B2 |
| 8987451 | Tsai | Mar 2015 | B2 |
| 9059412 | Zeng | Jun 2015 | B2 |
| 9076974 | Li | Jul 2015 | B2 |
| 9082989 | Li | Jul 2015 | B2 |
| 9203039 | Li | Dec 2015 | B2 |
| 9221857 | Li | Dec 2015 | B2 |
| 9224963 | Li | Dec 2015 | B2 |
| 9238668 | Li | Jan 2016 | B2 |
| 9312502 | Li | Apr 2016 | B2 |
| 9312505 | Brooks | Apr 2016 | B2 |
| 9318725 | Li | Apr 2016 | B2 |
| 9324957 | Li | Apr 2016 | B2 |
| 9382273 | Li | Jul 2016 | B2 |
| 9385329 | Li | Jul 2016 | B2 |
| 9425415 | Li | Aug 2016 | B2 |
| 9461254 | Tsai | Oct 2016 | B2 |
| 9493698 | Beers | Nov 2016 | B2 |
| 9502671 | Jian | Nov 2016 | B2 |
| 9550801 | Li | Jan 2017 | B2 |
| 9598449 | Li | Mar 2017 | B2 |
| 9617291 | Li | Apr 2017 | B2 |
| 9666822 | Forrest | May 2017 | B2 |
| 9673409 | Li | Jun 2017 | B2 |
| 9698359 | Li | Jul 2017 | B2 |
| 9711739 | Li | Jul 2017 | B2 |
| 9711741 | Li | Jul 2017 | B2 |
| 9711742 | Li | Jul 2017 | B2 |
| 9735397 | Riegel | Aug 2017 | B2 |
| 9755163 | Li | Sep 2017 | B2 |
| 9818959 | Li | Nov 2017 | B2 |
| 9865825 | Li | Jan 2018 | B2 |
| 9879039 | Li | Jan 2018 | B2 |
| 9882150 | Li | Jan 2018 | B2 |
| 9899614 | Li | Feb 2018 | B2 |
| 9920242 | Li | Mar 2018 | B2 |
| 9923155 | Li | Mar 2018 | B2 |
| 9941479 | Li | Apr 2018 | B2 |
| 9947881 | Li | Apr 2018 | B2 |
| 9985224 | Li | May 2018 | B2 |
| 10020455 | Li | Jul 2018 | B2 |
| 10033003 | Li | Jul 2018 | B2 |
| 10056564 | Li | Aug 2018 | B2 |
| 10056567 | Li | Aug 2018 | B2 |
| 10158091 | Li | Dec 2018 | B2 |
| 10177323 | Li | Jan 2019 | B2 |
| 10211411 | Li | Feb 2019 | B2 |
| 10211414 | Li | Feb 2019 | B2 |
| 10263197 | Li | Apr 2019 | B2 |
| 10294417 | Li | May 2019 | B2 |
| 10392387 | Li | Aug 2019 | B2 |
| 10411202 | Li | Sep 2019 | B2 |
| 10414785 | Li | Sep 2019 | B2 |
| 10516117 | Li | Dec 2019 | B2 |
| 10566553 | Li | Feb 2020 | B2 |
| 10566554 | Li | Feb 2020 | B2 |
| 10615349 | Li | Apr 2020 | B2 |
| 10622571 | Li | Apr 2020 | B2 |
| 10727422 | Li | Jul 2020 | B2 |
| 10745615 | Li | Aug 2020 | B2 |
| 10790457 | Li | Sep 2020 | B2 |
| 10793546 | Li | Oct 2020 | B2 |
| 10804475 | Zeng | Oct 2020 | B2 |
| 10804476 | Li | Oct 2020 | B2 |
| 10822363 | Li | Nov 2020 | B2 |
| 10836785 | Li | Nov 2020 | B2 |
| 10851106 | Li | Dec 2020 | B2 |
| 10886478 | Li | Jan 2021 | B2 |
| 10930865 | Li | Feb 2021 | B2 |
| 10937976 | Li | Mar 2021 | B2 |
| 10944064 | Li | Mar 2021 | B2 |
| 10964897 | Li | Mar 2021 | B2 |
| 10991897 | Li | Apr 2021 | B2 |
| 10995108 | Li | May 2021 | B2 |
| 11011712 | Li | May 2021 | B2 |
| 11063228 | Li | Jul 2021 | B2 |
| 11101435 | Li | Aug 2021 | B2 |
| 11114626 | Li | Sep 2021 | B2 |
| 11121328 | Li | Sep 2021 | B2 |
| 11145830 | Li | Oct 2021 | B2 |
| 11183670 | Li | Nov 2021 | B2 |
| 11594688 | Li | Feb 2023 | B2 |
| 20010019782 | Igarashi | Sep 2001 | A1 |
| 20020068190 | Tsuboyama | Jun 2002 | A1 |
| 20030062519 | Yamazaki | Apr 2003 | A1 |
| 20030180574 | Huang | Sep 2003 | A1 |
| 20030186077 | Chen | Oct 2003 | A1 |
| 20040230061 | Seo | Nov 2004 | A1 |
| 20050037232 | Tyan | Feb 2005 | A1 |
| 20050139810 | Kuehl | Jun 2005 | A1 |
| 20050170207 | Ma | Aug 2005 | A1 |
| 20050260446 | Mackenzie | Nov 2005 | A1 |
| 20060024522 | Thompson | Feb 2006 | A1 |
| 20060032528 | Wang | Feb 2006 | A1 |
| 20060066228 | Antoniadis | Mar 2006 | A1 |
| 20060073359 | Ise | Apr 2006 | A1 |
| 20060094875 | Itoh | May 2006 | A1 |
| 20060127696 | Stossel | Jun 2006 | A1 |
| 20060182992 | Nii | Aug 2006 | A1 |
| 20060202197 | Nakayama | Sep 2006 | A1 |
| 20060210831 | Sano | Sep 2006 | A1 |
| 20060255721 | Igarashi | Nov 2006 | A1 |
| 20060263635 | Ise | Nov 2006 | A1 |
| 20060286406 | Igarashi | Dec 2006 | A1 |
| 20070057630 | Nishita | Mar 2007 | A1 |
| 20070059551 | Yamazaki | Mar 2007 | A1 |
| 20070082284 | Stoessel | Apr 2007 | A1 |
| 20070103060 | Itoh | May 2007 | A1 |
| 20070160905 | Morishita | Jul 2007 | A1 |
| 20070252140 | Limmert | Nov 2007 | A1 |
| 20080001530 | Ise | Jan 2008 | A1 |
| 20080036373 | Itoh | Feb 2008 | A1 |
| 20080054799 | Satou | Mar 2008 | A1 |
| 20080079358 | Satou | Apr 2008 | A1 |
| 20080102310 | Thompson | May 2008 | A1 |
| 20080111476 | Choi | May 2008 | A1 |
| 20080241518 | Satou | Oct 2008 | A1 |
| 20080241589 | Fukunaga | Oct 2008 | A1 |
| 20080269491 | Jabbour | Oct 2008 | A1 |
| 20080315187 | Bazan | Dec 2008 | A1 |
| 20090026936 | Satou | Jan 2009 | A1 |
| 20090026939 | Kinoshita | Jan 2009 | A1 |
| 20090032989 | Karim | Feb 2009 | A1 |
| 20090039768 | Igarashi | Feb 2009 | A1 |
| 20090079340 | Kinoshita | Mar 2009 | A1 |
| 20090126796 | Yang | May 2009 | A1 |
| 20090128008 | Ise | May 2009 | A1 |
| 20090136779 | Cheng | May 2009 | A1 |
| 20090153045 | Kinoshita | Jun 2009 | A1 |
| 20090167167 | Aoyama | Jul 2009 | A1 |
| 20090205713 | Mitra | Aug 2009 | A1 |
| 20090218561 | Kitamura | Sep 2009 | A1 |
| 20090261721 | Murakami | Oct 2009 | A1 |
| 20090267500 | Kinoshita | Oct 2009 | A1 |
| 20100000606 | Thompson | Jan 2010 | A1 |
| 20100013386 | Thompson | Jan 2010 | A1 |
| 20100043876 | Tuttle | Feb 2010 | A1 |
| 20100093119 | Shimizu | Apr 2010 | A1 |
| 20100127246 | Nakayama | May 2010 | A1 |
| 20100141127 | Xia | Jun 2010 | A1 |
| 20100147386 | Benson-Smith | Jun 2010 | A1 |
| 20100171111 | Takada | Jul 2010 | A1 |
| 20100171418 | Kinoshita | Jul 2010 | A1 |
| 20100200051 | Triani | Aug 2010 | A1 |
| 20100204467 | Lamarque | Aug 2010 | A1 |
| 20100270540 | Chung | Oct 2010 | A1 |
| 20100288362 | Hatwar | Nov 2010 | A1 |
| 20100297522 | Creeth | Nov 2010 | A1 |
| 20100301315 | Masui | Dec 2010 | A1 |
| 20100307594 | Zhu | Dec 2010 | A1 |
| 20110028723 | Li | Feb 2011 | A1 |
| 20110049496 | Fukuzaki | Mar 2011 | A1 |
| 20110062858 | Yersin | Mar 2011 | A1 |
| 20110132440 | Sivarajan | Jun 2011 | A1 |
| 20110217544 | Young | Sep 2011 | A1 |
| 20110227058 | Masui | Sep 2011 | A1 |
| 20110301351 | Li | Dec 2011 | A1 |
| 20120024383 | Kaiho | Feb 2012 | A1 |
| 20120025588 | Humbert | Feb 2012 | A1 |
| 20120039323 | Hirano | Feb 2012 | A1 |
| 20120095232 | Li | Apr 2012 | A1 |
| 20120108806 | Li | May 2012 | A1 |
| 20120146012 | Limmert | Jun 2012 | A1 |
| 20120181528 | Takada | Jul 2012 | A1 |
| 20120199823 | Molt | Aug 2012 | A1 |
| 20120202997 | Parham | Aug 2012 | A1 |
| 20120204960 | Kato | Aug 2012 | A1 |
| 20120215001 | Li | Aug 2012 | A1 |
| 20120223634 | Xia | Sep 2012 | A1 |
| 20120264938 | Li | Oct 2012 | A1 |
| 20120273736 | James | Nov 2012 | A1 |
| 20120302753 | Li | Nov 2012 | A1 |
| 20130048963 | Beers | Feb 2013 | A1 |
| 20130082245 | Kottas | Apr 2013 | A1 |
| 20130137870 | Li | May 2013 | A1 |
| 20130168656 | Tsai | Jul 2013 | A1 |
| 20130172561 | Tsai | Jul 2013 | A1 |
| 20130200340 | Otsu | Aug 2013 | A1 |
| 20130203996 | Li | Aug 2013 | A1 |
| 20130237706 | Li | Sep 2013 | A1 |
| 20130341600 | Lin | Dec 2013 | A1 |
| 20140014922 | Lin | Jan 2014 | A1 |
| 20140014931 | Riegel | Jan 2014 | A1 |
| 20140027733 | Zeng | Jan 2014 | A1 |
| 20140042475 | Park | Feb 2014 | A1 |
| 20140066628 | Li | Mar 2014 | A1 |
| 20140073798 | Li | Mar 2014 | A1 |
| 20140084261 | Brooks | Mar 2014 | A1 |
| 20140114072 | Li | Apr 2014 | A1 |
| 20140147996 | Vogt | May 2014 | A1 |
| 20140148594 | Li | May 2014 | A1 |
| 20140191206 | Cho | Jul 2014 | A1 |
| 20140203248 | Zhou | Jul 2014 | A1 |
| 20140249310 | Li | Sep 2014 | A1 |
| 20140326960 | Kim | Nov 2014 | A1 |
| 20140330019 | Li | Nov 2014 | A1 |
| 20140364605 | Li | Dec 2014 | A1 |
| 20150008419 | Li | Jan 2015 | A1 |
| 20150018558 | Li | Jan 2015 | A1 |
| 20150028323 | Xia | Jan 2015 | A1 |
| 20150060804 | Kanitz | Mar 2015 | A1 |
| 20150069334 | Xia | Mar 2015 | A1 |
| 20150105556 | Li | Apr 2015 | A1 |
| 20150123047 | Maltenberger | May 2015 | A1 |
| 20150162552 | Li | Jun 2015 | A1 |
| 20150194616 | Li | Jul 2015 | A1 |
| 20150207086 | Li | Jul 2015 | A1 |
| 20150228914 | Li | Aug 2015 | A1 |
| 20150274762 | Li | Oct 2015 | A1 |
| 20150287938 | Li | Oct 2015 | A1 |
| 20150311456 | Li | Oct 2015 | A1 |
| 20150318500 | Li | Nov 2015 | A1 |
| 20150349279 | Li | Dec 2015 | A1 |
| 20150380666 | Szigethy | Dec 2015 | A1 |
| 20160028028 | Li | Jan 2016 | A1 |
| 20160028029 | Li | Jan 2016 | A1 |
| 20160043331 | Li | Feb 2016 | A1 |
| 20160072082 | Brooks | Mar 2016 | A1 |
| 20160130225 | Tasaki | May 2016 | A1 |
| 20160133861 | Li | May 2016 | A1 |
| 20160133862 | Li | May 2016 | A1 |
| 20160181529 | Tsai | Jun 2016 | A1 |
| 20160194344 | Li | Jul 2016 | A1 |
| 20160197285 | Zeng | Jul 2016 | A1 |
| 20160197291 | Li | Jul 2016 | A1 |
| 20160204358 | Stoessel | Jul 2016 | A1 |
| 20160285015 | Li | Sep 2016 | A1 |
| 20160359120 | Li | Dec 2016 | A1 |
| 20160359125 | Li | Dec 2016 | A1 |
| 20170005278 | Li | Jan 2017 | A1 |
| 20170012224 | Li | Jan 2017 | A1 |
| 20170040555 | Li | Feb 2017 | A1 |
| 20170047533 | Li | Feb 2017 | A1 |
| 20170066792 | Li | Mar 2017 | A1 |
| 20170069855 | Li | Mar 2017 | A1 |
| 20170077420 | Li | Mar 2017 | A1 |
| 20170125708 | Li | May 2017 | A1 |
| 20170267923 | Li | Sep 2017 | A1 |
| 20170271611 | Li | Sep 2017 | A1 |
| 20170301871 | Li | Oct 2017 | A1 |
| 20170305881 | Li | Oct 2017 | A1 |
| 20170309943 | Angell | Oct 2017 | A1 |
| 20170331056 | Li | Nov 2017 | A1 |
| 20170342098 | Li | Nov 2017 | A1 |
| 20170373260 | Li | Dec 2017 | A1 |
| 20180006246 | Li | Jan 2018 | A1 |
| 20180013096 | Hamada | Jan 2018 | A1 |
| 20180037812 | Pegington | Feb 2018 | A1 |
| 20180052366 | Hao | Feb 2018 | A1 |
| 20180053904 | Li | Feb 2018 | A1 |
| 20180062084 | Watabe | Mar 2018 | A1 |
| 20180130960 | Li | May 2018 | A1 |
| 20180138428 | Li | May 2018 | A1 |
| 20180148464 | Li | May 2018 | A1 |
| 20180159051 | Li | Jun 2018 | A1 |
| 20180166655 | Li | Jun 2018 | A1 |
| 20180175329 | Li | Jun 2018 | A1 |
| 20180194790 | Li | Jul 2018 | A1 |
| 20180198081 | Zeng | Jul 2018 | A1 |
| 20180219161 | Li | Aug 2018 | A1 |
| 20180226592 | Li | Aug 2018 | A1 |
| 20180226593 | Li | Aug 2018 | A1 |
| 20180277777 | Li | Sep 2018 | A1 |
| 20180301641 | Li | Oct 2018 | A1 |
| 20180312750 | Li | Nov 2018 | A1 |
| 20180331307 | Li | Nov 2018 | A1 |
| 20180334459 | Li | Nov 2018 | A1 |
| 20180337345 | Li | Nov 2018 | A1 |
| 20180337349 | Li | Nov 2018 | A1 |
| 20180337350 | Li | Nov 2018 | A1 |
| 20180353771 | Kim | Dec 2018 | A1 |
| 20190013485 | Li | Jan 2019 | A1 |
| 20190058137 | Ko | Feb 2019 | A1 |
| 20190067602 | Li | Feb 2019 | A1 |
| 20190109288 | Li | Apr 2019 | A1 |
| 20190119312 | Chen | Apr 2019 | A1 |
| 20190157352 | Li | May 2019 | A1 |
| 20190194536 | Li | Jun 2019 | A1 |
| 20190221757 | Tarran | Jul 2019 | A1 |
| 20190259963 | Li | Aug 2019 | A1 |
| 20190276485 | Li | Sep 2019 | A1 |
| 20190312217 | Li | Oct 2019 | A1 |
| 20190367546 | Li | Dec 2019 | A1 |
| 20190389893 | Li | Dec 2019 | A1 |
| 20200006678 | Li | Jan 2020 | A1 |
| 20200055885 | Tarran | Feb 2020 | A1 |
| 20200071330 | Li | Mar 2020 | A1 |
| 20200075868 | Li | Mar 2020 | A1 |
| 20200119288 | Li | Apr 2020 | A1 |
| 20200119289 | Lin | Apr 2020 | A1 |
| 20200140471 | Chen | May 2020 | A1 |
| 20200152891 | Li | May 2020 | A1 |
| 20200227656 | Li | Jul 2020 | A1 |
| 20200227660 | Li | Jul 2020 | A1 |
| 20200239505 | Li | Jul 2020 | A1 |
| 20200243776 | Li | Jul 2020 | A1 |
| 20200287153 | Li | Sep 2020 | A1 |
| 20200332185 | Li | Oct 2020 | A1 |
| 20200365819 | Seo | Nov 2020 | A1 |
| 20200373505 | Li | Nov 2020 | A1 |
| 20200403167 | Li | Dec 2020 | A1 |
| 20210024526 | Li | Jan 2021 | A1 |
| 20210024559 | Li | Jan 2021 | A1 |
| 20210047296 | Li | Feb 2021 | A1 |
| 20210091316 | Li | Mar 2021 | A1 |
| 20210104687 | Li | Apr 2021 | A1 |
| 20210111355 | Li | Apr 2021 | A1 |
| 20210126208 | Li | Apr 2021 | A1 |
| 20210193936 | Li | Jun 2021 | A1 |
| 20210193947 | Li | Jun 2021 | A1 |
| 20210206785 | Hamze | Jul 2021 | A1 |
| 20210217973 | Li | Jul 2021 | A1 |
| 20210230198 | Li | Jul 2021 | A1 |
| 20210261589 | Li | Aug 2021 | A1 |
| 20210273182 | Li | Sep 2021 | A1 |
| 20210292351 | Macinnis | Sep 2021 | A1 |
| 20210376260 | Li | Dec 2021 | A1 |
| 20220059786 | Seo | Feb 2022 | A1 |
| Number | Date | Country |
|---|---|---|
| 1680366 | Oct 2005 | CN |
| 1777663 | May 2006 | CN |
| 1894267 | Jan 2007 | CN |
| 1894269 | Jan 2007 | CN |
| 101142223 | Mar 2008 | CN |
| 101667626 | Mar 2010 | CN |
| 102449108 | May 2012 | CN |
| 102892860 | Jan 2013 | CN |
| 102971396 | Mar 2013 | CN |
| 103102372 | May 2013 | CN |
| 104232076 | Dec 2014 | CN |
| 104377231 | Feb 2015 | CN |
| 104576934 | Apr 2015 | CN |
| 104693243 | Jun 2015 | CN |
| 105367605 | Mar 2016 | CN |
| 105418591 | Mar 2016 | CN |
| 106783922 | May 2017 | CN |
| 1617493 | Jan 2006 | EP |
| 1808052 | Jul 2007 | EP |
| 1874893 | Jan 2008 | EP |
| 1874894 | Jan 2008 | EP |
| 1919928 | May 2008 | EP |
| 1968131 | Sep 2008 | EP |
| 2020694 | Feb 2009 | EP |
| 2036907 | Mar 2009 | EP |
| 2096690 | Sep 2009 | EP |
| 2112213 | Oct 2009 | EP |
| 2417217 | Feb 2012 | EP |
| 2684932 | Jan 2014 | EP |
| 2711999 | Mar 2014 | EP |
| 3032293 | Jun 2016 | EP |
| 2002010505 | Jan 2002 | JP |
| 2002105055 | Apr 2002 | JP |
| 2003342284 | Dec 2003 | JP |
| 2005031073 | Feb 2005 | JP |
| 2005267557 | Sep 2005 | JP |
| 2005310733 | Nov 2005 | JP |
| 2006047240 | Feb 2006 | JP |
| 2006232784 | Sep 2006 | JP |
| 2006242080 | Sep 2006 | JP |
| 2006242081 | Sep 2006 | JP |
| 2006256999 | Sep 2006 | JP |
| 2006257238 | Sep 2006 | JP |
| 2006261623 | Sep 2006 | JP |
| 2006290988 | Oct 2006 | JP |
| 2006313796 | Nov 2006 | JP |
| 2006332622 | Dec 2006 | JP |
| 2006351638 | Dec 2006 | JP |
| 2007019462 | Jan 2007 | JP |
| 2007031678 | Feb 2007 | JP |
| 2007042875 | Feb 2007 | JP |
| 2007051243 | Mar 2007 | JP |
| 2007053132 | Mar 2007 | JP |
| 2007066581 | Mar 2007 | JP |
| 2007073620 | Mar 2007 | JP |
| 2007073845 | Mar 2007 | JP |
| 2007073900 | Mar 2007 | JP |
| 2007080593 | Mar 2007 | JP |
| 2007080677 | Mar 2007 | JP |
| 2007088105 | Apr 2007 | JP |
| 2007088164 | Apr 2007 | JP |
| 2007096259 | Apr 2007 | JP |
| 2007099765 | Apr 2007 | JP |
| 2007110067 | Apr 2007 | JP |
| 2007110102 | Apr 2007 | JP |
| 2007519614 | Jul 2007 | JP |
| 2007258550 | Oct 2007 | JP |
| 2007324309 | Dec 2007 | JP |
| 2008010353 | Jan 2008 | JP |
| 2008091860 | Apr 2008 | JP |
| 2008103535 | May 2008 | JP |
| 2008108617 | May 2008 | JP |
| 2008109085 | May 2008 | JP |
| 2008109103 | May 2008 | JP |
| 2008116343 | May 2008 | JP |
| 2008117545 | May 2008 | JP |
| 2008160087 | Jul 2008 | JP |
| 2008198801 | Aug 2008 | JP |
| 2008270729 | Nov 2008 | JP |
| 2008270736 | Nov 2008 | JP |
| 2008310220 | Dec 2008 | JP |
| 2009016184 | Jan 2009 | JP |
| 2009016579 | Jan 2009 | JP |
| 2009032977 | Feb 2009 | JP |
| 2009032988 | Feb 2009 | JP |
| 2009059997 | Mar 2009 | JP |
| 2009076509 | Apr 2009 | JP |
| 2009161524 | Jul 2009 | JP |
| 2009247171 | Oct 2009 | JP |
| 2009266943 | Nov 2009 | JP |
| 2009267171 | Nov 2009 | JP |
| 2009267244 | Nov 2009 | JP |
| 2009272339 | Nov 2009 | JP |
| 2009283891 | Dec 2009 | JP |
| 4460952 | May 2010 | JP |
| 2010135689 | Jun 2010 | JP |
| 2010171205 | Aug 2010 | JP |
| 2011071452 | Apr 2011 | JP |
| 2012074444 | Apr 2012 | JP |
| 2012079895 | Apr 2012 | JP |
| 2012079898 | Apr 2012 | JP |
| 5604505 | Sep 2012 | JP |
| 2012522843 | Sep 2012 | JP |
| 2012207231 | Oct 2012 | JP |
| 2012222255 | Nov 2012 | JP |
| 2012231135 | Nov 2012 | JP |
| 2013023500 | Feb 2013 | JP |
| 2013048256 | Mar 2013 | JP |
| 2013053149 | Mar 2013 | JP |
| 2013525436 | Jun 2013 | JP |
| 2014019701 | Feb 2014 | JP |
| 2014058504 | Apr 2014 | JP |
| 2014520096 | Aug 2014 | JP |
| 2012709899 | Nov 2014 | JP |
| 2014221807 | Nov 2014 | JP |
| 2014239225 | Dec 2014 | JP |
| 2015081257 | Apr 2015 | JP |
| 20060011537 | Feb 2006 | KR |
| 20060015371 | Feb 2006 | KR |
| 20060115371 | Nov 2006 | KR |
| 20070061830 | Jun 2007 | KR |
| 20070112465 | Nov 2007 | KR |
| 20130043460 | Apr 2013 | KR |
| 101338250 | Dec 2013 | KR |
| 20140052501 | May 2014 | KR |
| 200701835 | Jan 2007 | TW |
| 201249851 | Dec 2012 | TW |
| 201307365 | Feb 2013 | TW |
| 201710277 | Mar 2017 | TW |
| 0070655 | Nov 2000 | WO |
| 2000070655 | Nov 2000 | WO |
| 2004003108 | Jan 2004 | WO |
| 2004070655 | Aug 2004 | WO |
| 2004085450 | Oct 2004 | WO |
| 2004108857 | Dec 2004 | WO |
| 2005042444 | May 2005 | WO |
| 2005042550 | May 2005 | WO |
| 2005113704 | Dec 2005 | WO |
| 2006033440 | Mar 2006 | WO |
| 2006067074 | Jun 2006 | WO |
| 2006081780 | Aug 2006 | WO |
| 2006098505 | Sep 2006 | WO |
| 2006113106 | Oct 2006 | WO |
| 2006115299 | Nov 2006 | WO |
| 2006115301 | Nov 2006 | WO |
| 2007034985 | Mar 2007 | WO |
| 2007069498 | Jun 2007 | WO |
| 2008054578 | May 2008 | WO |
| 2008066192 | Jun 2008 | WO |
| 2008066195 | Jun 2008 | WO |
| 2008066196 | Jun 2008 | WO |
| 2008101842 | Aug 2008 | WO |
| 2008117889 | Oct 2008 | WO |
| 2008123540 | Oct 2008 | WO |
| 2008131932 | Nov 2008 | WO |
| 2009003455 | Jan 2009 | WO |
| 2009008277 | Jan 2009 | WO |
| 2009011327 | Jan 2009 | WO |
| 2009017211 | Feb 2009 | WO |
| 2009023667 | Feb 2009 | WO |
| 2009086209 | Jul 2009 | WO |
| 2009111299 | Sep 2009 | WO |
| 2010007098 | Jan 2010 | WO |
| 2010056669 | May 2010 | WO |
| 2010093176 | Aug 2010 | WO |
| 2010105141 | Sep 2010 | WO |
| 2010118026 | Oct 2010 | WO |
| 2011064335 | Jun 2011 | WO |
| 2011070989 | Jun 2011 | WO |
| 2011089163 | Jul 2011 | WO |
| 2011137429 | Nov 2011 | WO |
| 2011137431 | Nov 2011 | WO |
| 2012074909 | Jun 2012 | WO |
| 2012112853 | Aug 2012 | WO |
| 2012116231 | Aug 2012 | WO |
| 2012142387 | Oct 2012 | WO |
| 2012162488 | Nov 2012 | WO |
| 2012163471 | Dec 2012 | WO |
| 2013130483 | Sep 2013 | WO |
| 2014009310 | Jan 2014 | WO |
| 2014016611 | Jan 2014 | WO |
| 2014031977 | Feb 2014 | WO |
| 2014047616 | Mar 2014 | WO |
| 2014109814 | Jul 2014 | WO |
| 2014208271 | Dec 2014 | WO |
| 2015027060 | Feb 2015 | WO |
| 2015131158 | Sep 2015 | WO |
| 2016025921 | Feb 2016 | WO |
| 2016029137 | Feb 2016 | WO |
| 2016029186 | Feb 2016 | WO |
| 2016088354 | Jun 2016 | WO |
| 2016197019 | Dec 2016 | WO |
| 2017117935 | Jul 2017 | WO |
| 2018071697 | Apr 2018 | WO |
| 2018140765 | Aug 2018 | WO |
| 2019079505 | Apr 2019 | WO |
| 2019079508 | Apr 2019 | WO |
| 2019079509 | Apr 2019 | WO |
| 2019236541 | Dec 2019 | WO |
| 2020018476 | Jan 2020 | WO |
| Entry |
|---|
| Adachi, C. et al., “High-efficiency organic electrophosphorescent devices with tris(2-phenylpyridine)iridium doped into electron-transporting materials”, Applied Physics Letters, Aug. 2000, vol. 77, No. 6, pp. 904-906 <DOI:10.1063/1.1306639>. |
| Ayan Maity et al., “Room-temperature synthesis of cyclometalated iridium(III) complexes; kinetic isomers and reactive functionalities” Chem. Sci., vol. 4, pp. 1175-1181 (2013). |
| Baldo et al., “Very High-Efficiency Green Organic Light-Emitting Devices Based on Electrophosphorescence”, Appl Phys Lett, 75(3):4-6 (1999). |
| Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, Sep. 10, 1998, pp. 151-154. |
| Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Applied Physics Letters, vol. 75, No. 1, Jul. 5, 1999, pp. 4-6. |
| Baldo, M. et al., “Excitonic singlet-triplet ratio in a semiconducting organic thin film”, Physical Review B, Nov. 1999, vol. 60, No. 20, pp. 14422-14428 <DOI: 10.1103/PhysRevB.60.14422>. |
| Baldo, M. et al., “High-efficiency fluorescent organic light-emitting devices using a phosphorescent sensitizer”, Nature, Feb. 2000, vol. 403, pp. 750-753. |
| Barry O'Brien et al.: White organic light emitting diodes using Pt-based red, green and blue phosphorescent dopants. Proc. SPIE, vol. 8829, pp. 1-6, Aug. 25, 2013. |
| Barry O'Brien et al., “High efficiency white organic light emitting diodes employing blue and red platinum emitters,” Journal of Photonics for Energy, vol. 4, 2014, pp. 043597-1-8. |
| Berson et al. (2007). “Poly(3-hexylthiophene) fibers for photovoltaic applications,” Adv. Funct. Mat., 17, 1377-84. |
| Bouman et al. (1994). “Chiroptical properties of regioregular chiral polythiophenes,” Mol. Cryst. Liq. Cryst., 256, 439-48. |
| Brian W. D'Andrade et al., “Controlling Exciton Diffusion in Multilayer White Phosphorescent Organic Light Emitting Devices”, Adv. Mater., vol. 14, No. 2, Jan. 16, 2002, pp. 147-151. |
| Bronner; “Dipyrrin based luminescent cyclometallated palladium and platinum complexes”, Dalton Trans., 2010, 39, 180-184. DOI: 10.1039/b908424j (Year: 2010) (5 pages). |
| Brooks, J. et al., “Synthesis and Characterization of Phosphorescent Cyclometalated Platinum Complexes”, Inorganic Chemistry, May 2002, vol. 41, No. 12, pp. 3055-3066 <DOI:10.1021/ic0255508>. |
| Brown, A. et al., “Optical spectroscopy of triplet excitons and charged excitations in poly(p-phenylenevinylene) light-emitting diodes”, Chemical Physics Letters, Jul. 1993, vol. 210, No. 1-3, pp. 61-66 <DOI:10.1016/0009-2614(93)89100-V>. |
| Burroughes, J. et al., “Light-emitting diodes based on conjugated polymers”, Nature, Oct. 1990, vol. 347, pp. 539-541. |
| Campbell et al. (2008). “Low-temperature control of nanoscale morphology for high performance polymer photovoltaics,” Nano Lett., 8, 3942-47. |
| Chen, F. et al., “High-performance polymer light-emitting diodes doped with a red phosphorescent iridium complex”, Applied Physics Letters, Apr. 2002 [available online Mar. 2002], vol. 80, No. 13, pp. 2308-2310 <10.1063/1.1462862>. |
| Chen, X., et al., “Fluorescent Chemosensors Based on Spiroring-Opening of Xanthenes and Related Derivatives”, Chemical Reviews, 2012 [available online Oct. 2011], vol. 112, No. 3, pp. 1910-1956 <DOI:10.1021/cr200201z>. |
| Chew, S. et al: Photoluminescence and electroluminescence of a new blue-emitting homoleptic iridium complex. Applied Phys. Letters; vol. 88, pp. 093510-1-093510-3, 2006. |
| Chi et al.; Transition-metal phosphors with cyclometalating ligands: fundamentals and applications, Chemical Society Reviews, vol. 39, No. 2, Feb. 2010, pp. 638-655. |
| Chi-Ming Che et al. “Photophysical Properties and OLEO Applications of Phosphorescent Platinum(II) Schiff Base Complexes,” Chem. Eur. J., vol. 16, 2010, pp. 233-247. |
| Chow; “Strongly Phosphorescent Palladium (II) Complexes of Tetradentate Ligands with Mixed Oxygen, Carbon, and Nitrogen Donor Atoms: Photophysics, Photochemistry, and Applications”, Angew. Chem. Int. Ed. 2013, 52, 11775-11779. DOI: 10.1002/anie.201305590 (Year: 2013) (5 pages). |
| Christoph Ulbricht et al., “Synthesis and Characterization of Oxetane-Functionalized Phosphorescent Ir(III)-Complexes”, Macromol. Chem. Phys. 2009, 210, pp. 531-541. |
| Coakley et al. (2004). “Conjugated polymer photovoltaic cells,” Chem. Mater., 16, 4533-4542. |
| Colombo, M. et al., “Synthesis and high-resolution optical spectroscopy of bis[2-(2-thienyl)pyridinato-C3,N′](2,2′-bipyridine)iridium(III)”, Inorganic Chemistry, Jul. 1993, vol. 32, No. 14, pp. 3081-3087 <DOI:10.1021/ic00066a019>. |
| D.F. O'Brien et al., “Improved energy transfer in electrophosphorescent devices,” Appl. Phys. Lett., vol. 74, No. 3, Jan. 18, 1999, pp. 442-444. |
| D'Andrade, B. et al., “Operational stability of electrophosphorescent devices containing p and n doped transport layers ”, Applied Physics Letters, Nov. 2003, vol. 83, No. 19, pp. 3858-3860 <DOI:10.1063/1.1624473>. |
| Dan Wang et al., “Carbazole and arylamine functionalized iridium complexes for efficient electro-phosphorescent light-emitting diodes”, Inorganica Chimica Acta 370 (2011) pp. 340-345. |
| Dileep A. K. Vezzu et al., “Highly Luminescent Tetradentate Bis-Cyclometalated Platinum Complexes: Design, Synthesis, Structure, Photophysics, and Electroluminescence Application,” Inorg. Chem., vol. 49, 2010, pp. 5107-5119. |
| Dorwald, Side Reactions in Organic Synthesis 2005, Wiley:VCH Weinheim Preface, pp. 1-15 & Chapter 1, pp. 279-308. |
| Dorwald; “Side Reactions in Organic Synthesis: A Guide to Successful Synthesis Design,” Chapter 1, 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Wienheim, 32 pages. |
| Dsouza, R., et al., “Fluorescent Dyes and Their Supramolecular Host/Guest Complexes with Macrocycles in Aqueous Solution”, Oct. 2011, vol. 111, No. 12, pp. 7941-7980 <DOI:10.1021/cr200213s>. |
| Eric Turner et al., “Cyclometalated Platinum Complexes with Luminescent Quantum Yields Approaching 100%,” Inorg. Chem., 2013, vol. 52, pp. 7344-7351. |
| Evan L. Williams et al., “Excimer-Based White Phosphorescent Organic Light Emitting Diodes with Nearly 100% Internal Quantum Efficiency,” Adv. Mater., vol. 19, 2007, pp. 197-202. |
| Finikova, M.A. et al., New Selective Synthesis of Substituted Tetrabenzoporphyris, Doklady Chemistry, 2003, vol. 391, No. 4-6, pp. 222-224. |
| Fuchs, C. et al., “Enhanced light emission from top-emitting organic light-emitting diodes by optimizing surface plasmon polariton losses”, arXiv, submitted Mar. 2015, 11 pages, arXiv:1503.01309. |
| Fuchs, C. et al., “Enhanced light emission from top-emitting organic light-emitting diodes by optimizing surface plasmon polariton losses”, Physical Review B, Dec. 2015, vol. 92, No. 24, pp. 245306-1-245306-10 <DOI:10.1103/PhysRevB.92.245306>. |
| Galanin et al. Synthesis and Properties of meso-Phenyl-Substituted Tetrabenzoazaporphines Magnesium Complexes. Russian Journal of Organic Chemistry (Translation of Zhurnal Organicheskoi Khimii) (2002), 38(8), 1200-1203. |
| Galanin et al., meso-Phenyltetrabenzoazaporphyrins and their zinc complexes. Synthesis and spectral properties, Russian Journal of General Chemistry (2005), 75(4), 651-655. |
| Gather, M. et al., “Recent advances in light outcoupling from white organic light-emitting diodes,” Journal of Photonics for Energy, May 2015, vol. 5, No. 1, 057607-1-057607-20 <DOI:10.1117/1.JPE.5.057607>. |
| Glauco Ponterini et al., “Comparison of Radiationless Decay Processes in Osmium and Platinum Porphyrins,” J. Am. Chem. Soc., vol. 105, No. 14, 1983, pp. 4639-4645. |
| Gong et al., Highly Selective Complexation of Metal Ions by the Self-Tuning Tetraazacalixpyridine macrocycles, Tetrahedron, 65(1): 87-92 (2009). |
| Gottumukkala, V. et al., Synthesis, cellular uptake and animal toxicity of a tetra carboranylphenyl N-tetrabenzoporphyr in, Bioorganic & Medicinal Chemistry, 2006, vol. 14, pp. 1871-1879. |
| Graf, A. et al., “Correlating the transition dipole moment orientation of phosphorescent emitter molecules in OLEDs with basic material properties”, Journal of Materials Chemistry C, Oct. 2014, vol. 2, No. 48, pp. 10298-10304 <DOI:10.1039/c4tc00997e>. |
| Guijie Li et al., “Efficient and stable red organic light emitting devices from a tetradentate cyclometalated platinum complex,” Organic Electronics, 2014, vol. 15 pp. 1862-1867. |
| Guijie Li et al., “Modifying Emission Spectral Bandwidth of Phosphorescent Platinum(II) Complexes Through Synthetic Control,” Inorg. Chem. 2017, 56, 8244-8256. |
| Guijie Li et al., Efficient and Stable White Organic Light-Emitting Diodes Employing a Single Emitter, Adv. Mater., 2014, vol. 26, pp. 2931-2936. |
| Hansen (1969). “The universality of the solubility parameter,” I & EC Product Research and Development, 8, 2-11. |
| Hatakeyama, T. et al., “Ultrapure Blue Thermally Activated Delayed Fluorescence Molecules: Efficient HOMO-LUMO Separation by the Multiple Resonance Effect”, Advanced Materials, Apr. 2016, vol. 28, No. 14, pp. 2777-2781, <DOI:10.1002/adma.201505491>. |
| Hirohiko Fukagawa et al., “Highly Efficient and Stable Red Phosphorescent Organic Light-Emitting Diodes Using Platinum Complexes,” Adv. Mater., 2012, vol. 24, pp. 5099-5103. |
| Hoe-Joo Seo et al., “Blue phosphorescent iridium(III) complexes containing carbazole-functionalized phenyl pyridine for organic light-emitting diodes: energy transfer from carbazolyl moieties to iridium(III) cores”, RSC Advances, 2011, 1, pp. 755-757. |
| Holmes, R. et al., “Efficient, deep-blue organic electrophosphorescence by guest charge trapping”, Applied Physics Letters, Nov. 2003 [available online Oct. 2003], vol. 83, No. 18, pp. 3818-3820 <DOI:10.1063/1.1624639>. |
| Huaijun Tang et al., “Novel yellow phosphorescent iridium complexes containing a carbazoleeoxadiazole unit used in polymeric light-emitting diodes”, Dyes and Pigments 91 (2011) pp. 413-421. |
| Imre et al (1996). “Liquid-liquid demixing ffrom solutions of polystyrene. 1. A review. 2. Improved correlation with solvent properties,” J. Phys. Chem. Ref. Data, 25, 637-61. |
| Ivaylo Ivanov et al., “Comparison of the INDO band structures of polyacetylene, polythiophene, polyfuran, and polypyrrole,” Synthetic Metals, vol. 116, Issues 1-3, Jan. 1, 2001, pp. 111-114. |
| Jack W. Levell et al., “Carbazole/iridium dendrimer side-chain phosphorescent copolymers for efficient light emitting devices”, New J. Chem., 2012, vol. 36, pp. 407-413. |
| Jan Kalinowski et al., “Light-emitting devices based on organometallic platinum complexes as emitters,” Coordination Chemistry Reviews, vol. 255, 2011, pp. 2401-2425. |
| Jeong et al. (2010). “Improved efficiency of bulk heterojunction poly (3-hexylthiophene): [6,6]-phenyl-C61-butyric acid methyl ester photovoltaic devices using discotic liquid crystal additives,” Appl. Phys. Lett . . . 96, 183305. (3 pages). |
| Jeonghun Kwak et al., “Bright and Efficient Full-Color Colloidal Quantum Dot Light-Emitting Diodes Using an Inverted Device Structure,” Nano Letters 12, Apr. 2, 2012, pp. 2362-2366. |
| Ji Hyun Seo et al., “Efficient blue-green organic light-emitting diodes based on heteroleptic tris-cyclometalated iridium (III) complexes”. Thin Solid Films, vol. 517, pp. 1807-1810 (2009). |
| Kai Li et al., “Light-emitting platinum(II) complexes supported by tetradentate dianionic bis(N-heterocyclic carbene) ligands: towards robust blue electrophosphors,” Chem. Sci., 2013, vol. 4, pp. 2630-2644. |
| Ke Feng et al., “Norbornene-Based Copolymers Containing Platinum Complexes and Bis(carbazolyl)benzene Groups in Their Side-Chains,” Macromolecules, vol. 42, 2009, pp. 6855-6864. |
| Kim et al (2009). “Altering the thermodynamics of phase separation in inverted bulk-heterojunction organic solar cells,” Adv. Mater., 21, 3110-15. |
| Kim et al. (2005). “Device annealing effect in organic solar cells with blends of regioregular poly (3-hexylthiophene) and soluble fullerene,” Appl. Phys. Lett. 86, 063502. (3 pages). |
| Kim, HY. et al., “Crystal Organic Light-Emitting Diodes with Perfectly Oriented Non-Doped Pt-Based Emitting Layer”, Advanced Functional Materials, Feb. 2016, vol. 28, No. 13, pp. 2526-2532 <DOI:10.1002/adma.201504451>. |
| Kim, JJ., “Setting up the new efficiency limit of OLEDs; Abstract” [online], Electrical Engineering—Princeton University, Aug. 2014 [retrieved on Aug. 24, 2016], retrieved from the internet: <URL:http://ee.princeton.edu/events/setting-new-efficiency-limit-oled> 2 pages. |
| Kim, SY. et al., “Organic Light-Emitting Diodes with 30% External Quantum Efficiency Based on a Horizontally Oriented Emitter”, Advanced Functional Materials, Mar. 2013, vol. 23, No. 31, pp. 3896-3900 <DOI:10.1002/adfm.201300104 >. |
| Kroon et al. (2008). “Small bandgap olymers for organic solar cells,” Polymer Reviews, 48, 531-82. |
| Kwon-Hyeon Kim et al., “Controlling Emitting Dipole Orientation with Methyl Substituents on Main Ligand of Iridium Complexes for Highly Efficient Phosphorescent Organic Light-Emitting Diodes”, Adv. Optical Mater. 2015, 3, pp. 1191-1196. |
| Kwon-Hyeon Kim et al., “Crystal Organic Light-Emitting Diodes with Perfectly Oriented Non-Doped Pt-Based Emitting Layer”, Adv. Mater. 2016, 28, pp. 2526-2532. |
| Kwong, R. et al., “High operational stability of electrophosphorescent devices”, Applied Physics Letters, Jul. 2002 [available online Jun. 2002], vol. 81, No. 1, pp. 162-164 <DOI:10.1063/1.1489503>. |
| Lamansky, S. et al., “Cyclometalated Ir complexes in polymer organic light-emitting devices”, Journal of Applied Physics, Aug. 2002 [available online Jul. 2002], vol. 92, No. 3, pp. 1570-1575 <10.1063/1.1491587>. |
| Lamansky, S. et al., “Synthesis and Characterization of Phosphorescent Cyclometalated Iridium Complexes”, Inorganic Chemistry, Mar. 2001, vol. 40, No. 7, pp. 1704-1711 <DOI:10.1021/ic0008969>. |
| Lampe, T. et al., “Dependence of Phosphorescent Emitter Orientation on Deposition Technique in Doped Organic Films”, Chemistry of Materials, Jan. 2016, vol. 28, pp. 712-715 <DOI:10.1021/acs.chemmater.5b04607>. |
| Lee et al. (2008). “Processing additives for inproved efficiency from bulk heterojunction solar cells,” J. Am. Chem. Soc, 130, 3619-23. |
| Li et al. (2005). “Investigation of annealing effects and film thickness dependence of polymer solar cells based on poly (3-hexylthiophene),” J. Appl. Phys., 98, 043704. (5 pages). |
| Li et al. (2007). “Solvent annealing effect in polymer solar cells based on poly(3-hexylthiophene) and methanofullerenes,” Adv. Funct. Mater, 17, 1636-44. |
| Li, J. et al., “Synthesis and characterization of cyclometalated Ir(III) complexes with pyrazolyl ancillary ligands”, Polyhedron, Jan. 2004, vol. 23, No. 2-3, pp. 419-428 <DOI: 10.1016/j.poly.2003.11.028>. |
| Li, J., “Efficient and Stable OLEDs Employing Square Planar Metal Complexes and Inorganic Nanoparticles”, in DOE SSL R&D Workshop (Raleigh, North Carolina, 2016), Feb. 2016, 15 pages. |
| Li, J., et al., “Synthetic Control of Excited-State Properties in Cyclometalated Ir(III) Complexes Using Ancillary Ligands”, Inorganic Chemistry, Feb. 2005, vol. 44, No. 6, pp. 1713-1727 <DOI:10.1021/ic048599h>. |
| Liang, et al. (2010). “For the bright future-bulk heterojunction polymer solar cells with power conversion efficiency of 7.4%,” Adv. Mater. 22, E135-38. |
| Lin, TA et al., “ Sky-Blue Organic Light Emitting Diode with 37% External Quantum Efficiency Using Thermally Activated Delayed Fluorescence from Spiroacridine-Triazine Hybrid”, Advanced Materials, Aug. 2016, vol. 28, No. 32, pp. 6876-6983 <DOI: 10.1002/adma.201601675>. |
| Maestri et al., “Absorption Spectra and Luminescence Properties of Isomeric Platinum (II) and Palladium (II) Complexes Containing 1,1′-Biphenyldiyl, 2-Phenylpyridine, and 2,2′-Bipyridine as Ligands,” Helvetica Chimica Acta, vol. 71, Issue 5, Aug. 10, 1988, pp. 1053-1059. |
| Marc Lepeltier et al., “Efficient blue green organic light-emitting devices based on a monofluorinated heteroleptic iridium(III) complex,” Synthetic Metals, vol. 199, 2015, pp. 139-146. |
| Markham, J. et al., “High-efficiency green phosphorescence from spin-coated single-layer dendrimer light-emitting diodes ”, Applied Physics Lettersm Apr. 2002, vol. 80, vol. 15, pp. 2645-2647 <DOI:10.1063/1.1469218>. |
| Matthew J. Jurow et al., “Understanding and predicting the orientation of heteroleptic phosphors in organic light-emitting materials”, Nature Materials, vol. 15, Jan. 2016, pp. 85-93. |
| Michl, J., “Relationship of bonding to electronic spectra”, Accounts of Chemical Research, May 1990, vol. 23, No. 5, pp. 127-128 <DOI:10.1021/ar00173a001>. |
| Miller, R. et al., “Polysilane high polymers”, Chemical Reviews, Sep. 1989, vol. 89, No. 6, pp. 1359-1410 <DOI:10.1021/cr00096a006>. |
| Morana et al. (2007). “Organic field-effect devices as tool to characterize the bipolar transport in polymer-fullerene blends: the case of P3HT-PCBM,” Adv. Funct. Mat., 17, 3274-83. |
| Moule et al. (2008). “Controlling morphology in Polymer-Fullerene mixtures,” Adv. Mater., 20, 240-45. |
| Murakami; JP 2007324309, English machine translation from EPO, dated Dec. 13, 2007, 89 pages. |
| Nazeeruddin, M. et al., “Highly Phosphorescence Iridium Complexes and Their Application in Organic Light-Emitting Devices”, Journal of the American Chemical Society, Jun. 2003, vol. 125, No. 29, pp. 8790-8797 <DOI:10.1021/ja021413y>. |
| Nicholas R. Evans et al., “Triplet Energy Back Transfer in Conjugated Polymers with Pendant Phosphorescent Iridium Complexes,” J. Am. Chem. Soc., vol. 128, 2006, pp. 6647-6656. |
| Nillson et al. (2007). “Morphology and phase segregation of spin-casted films of polyfluorene/PCBM Blends,” Macromolecules, 40, 8291-8301. |
| Office Action dated Jan. 24, 2020 for U.S. Appl. No. 15/984,036 (pp. 1-24). |
| Olynick et al. (2009). “The link between nanoscale feature development in a negative resist and the Hansen solubility sphere,” Journal of Polymer Science: Part B: Polymer Physics, 47, 2091-2105. |
| Peet et al. (2007). “Efficiency enhancement in low-bandgap polymer solar cells by processing with alkane dithiols,” Nature Materials, 6, 497-500. |
| Pivrikas et al. (2008). “Substituting the postproduction treatment for bulk-heterojunction solar cells using chemical additives,” Organic Electronics, 9, 775-82. |
| Pui Keong Chow et al., “Strongly Phosphorescent Palladium(II) Complexes of Tetradentate Ligands with Mixed Oxygen, Carbon, and Nitrogen Donor Atoms: Photophysics, Photochemistry, and Applications,” Angew. Chem. Int. Ed. 2013, 52, 11775-11779. |
| Pui-Keong Chow et al., “Highly luminescent palladium(II) complexes with sub-millisecond blue to green phosphorescent excited states. Photocatalysis and highly efficient PSF-OLEDs,” Chem. Sci., 2016, 7, 6083-6098. |
| Results from SciFinder Compound Search on Dec. 8, 2016. (17 pages). |
| Rui Zhu et al., “Color tuning based on a six-membered chelated iridium (III) complex with aza-aromatic ligand,” Chemistry Letters, vol. 34, No. 12, 2005, pp. 1668-1669. |
| Russell J. Holmes et al., “Blue and Near-UV Phosphorescence from Iridium Complexes with Cyclometalated Pyrazolyl or N-Heterocyclic Carbene Ligands,” Inorganic Chemistry, 2005, vol. 44, No. 22, pp. 7995-8003. |
| Sajoto, T. et al., “Temperature Dependence of Blue Phosphorescent Cyclometalated Ir(III) Complexes”, Journal of the American Chemical Society, Jun. 2009, vol. 131, No. 28, pp. 9813-9822 <DOI:10.1021/ja903317w>. |
| Sakai, Y. et al., “Simple model-free estimation of orientation order parameters of vacuum-deposited and spin-coated amorphous films used in organic light-emitting diodes”, Applied Physics Express, Aug. 2015, vol. 8, No. 9, pp. 096601-1-096601-4 <DOI:10.7567/APEX.8.096601>. |
| Saricifci et al. (1993). “Semiconducting polymerbuckminsterfullerene heterojunctions: diodes photodiodes, and photovoltaic cells,” Appl. Phys. Lett., 62, 585-87. |
| Satake et al., “Interconvertible Cationic and Neutral Pyridinylimidazole η3-Allylpalladium Complexes. Structural Assignment by 1H, 13C, and 15N NMR and X-ray Diffraction”, Organometallics, vol. 18, No. 24, 1999, pp. 5108-5111. |
| Saunders et al. (2008). “Nanoparticle-polymer photovoltaic cells,” Advances in Colloid and Interface Science, 138, 1-23. |
| Senes, A. et al., “Transition dipole moment orientation in films of solution processed fluorescent oligomers: investigating the influence of molecular anisotropy”, Journal of Materials Chemistry C, Jun. 2016, vol. 4, No. 26, pp. 6302-6308 <DOI: 10.1039/c5tc03481g>. |
| Shih-Chun Lo et al. “High-Triplet-Energy Dendrons: Enhancing the Luminescence of Deep Blue Phosphorescent Indium(III) Complexes” J. Am. Chem. Soc., vol. 131, 2009, pp. 16681-16688. |
| Shin et al. (2010). “Abrupt morphology change upon thermal annealing in Poly(3-hexathiophene)/soluble fullerene blend films for polymer solar cells,” Adv. Funct. Mater., 20, 748-54. |
| Shiro Koseki et al., “Spin-orbit coupling analyses of the geometrical effects on phosphorescence in Ir(ppy)3 and its derivatives”, J. Phys. Chem. C, vol. 117, pp. 5314-5327 (2013). |
| Shizuo Tokito et al. “Confinement of triplet energy on phosphorescent molecules for highly-efficient organic blue-light-emitting devices” Applied Physics Letters, vol. 83, No. 3, Jul. 21, 2003, pp. 569-571. |
| Stefan Bernhard, “The First Six Years: A Report,” Department of Chemistry, Princeton University, May 2008, 11 pages. |
| Stephen R. Forrest, “The path to ubiquitous and low-cost organic electronic appliances on plastic,” Nature, vol. 428, Apr. 29, 2004, pp. 911-918. |
| Steven C. F. Kui et al., “Robust phosphorescent platinum(II) complexes with tetradentate O∧N∧C∧N ligands: high efficiency OLEDs with excellent efficiency stability,” Chem. Commun., 2013, vol. 49, pp. 1497-1499. |
| Steven C. F. Kui et al., “Robust Phosphorescent Platinum(II) Complexes Containing Tetradentate O∧N∧C∧N Ligands: Excimeric Excited State and Application in Organic White-Light-Emitting Diodes,” Chem. Eur. J., 2013, vol. 19, pp. 69-73. |
| Strouse, G. et al., “Optical Spectroscopy of Single Crystal [Re(bpy)(CO)4](PF6): Mixing between Charge Transfer and Ligand Centered Excited States”, Inorganic Chemistry, Oct. 1995, vol. 34, No. 22, pp. 5578-5587 <DOI:10.1021/ic00126a031>. |
| Supporting Information: Xiao-Chun Hang et al., “Highly Efficient Blue-Emitting Cyclometalated Platinum(II) Complexes by Judicious Molecular Design,” Wiley-VCH 2013, 7 pages. |
| Sylvia Bettington et al. “Tris-Cyclometalated Iridium(III) Complexes of Carbazole(fluorenyl)pyridine Ligands: Synthesis, Redox and Photophysical Properties, and Electrophosphorescent Light-Emitting Diodes” Chemistry: A European Journal, 2007, vol. 13, pp. 1423-1431. |
| Tang, C. et al., “Organic electroluminescent diodes”, Applied Physics Letters, Jul. 1987, vol. 51, No. 12, pp. 913-915 <DOI: 10.1063/1.98799>. |
| Tsuoboyama, A. et al., “Homoleptic Cyclometalated Iridium Complexes with Highly Efficient Red Phosphorescence and Application to Organic Light-Emitting Diode”, Journal of the American Chemical Society, Sep. 2003, vol. 125, No. 42, pp. 12971-12979 <DOI:10.1021/ja034732d>. |
| Turro, N., “Modern Molecular Photochemistry” (Sausalito, California, University Science Books, 1991), p. 48. (3 pages). |
| Tyler Fleetham et al., “Efficient “pure” blue OLEDs employing tetradentate Pt complexes with a narrow spectral bandwidth,” Advanced Materials (Weinheim, Germany), Vo. 26, No. 41, 2014, pp. 7116-7121. |
| Tyler Fleetham et al., “Efficient Red-Emitting Platinum Complex with Long Operational Stability,” ACS Appl. Mater. Interfaces 2015, 7, 16240-16246. |
| V. Adamovich et al., “High efficiency single dopant white electrophosphorescent light emitting diodes”, New J. Chem, vol. 26, pp. 1171-1178. 2002. |
| V. Thamilarasan et al., “Green-emitting phosphorescent iridium(III) complex: Structural, photophysical and electrochemical properties,” Inorganica Chimica Acta, vol. 408, 2013, pp. 240-245. |
| Vanessa Wood et al., “Colloidal quantum dot light-emitting devices,” Nano Reviews 1, Jul. 2010, pp. 5202. (7 pages). |
| Vezzu, D. et al.: Highly luminescent tridentate platinum complexes featured in fused five-six-membered metallocycle and diminishing quenching. Inorganic Chem., vol. 50 (17), pp. 8261-8273, 2011. |
| Wang et al. (2010). “The development of nanoscale morphology in polymer: fullerene photovoltaic blends during solvent casting,” Soft Matter, 6, 4128-4134. |
| Wang et al., C(aryl)-C(alkyl) bond formation from Cu(CI04)2-mediated oxidative cross coupling reaction between arenes and alkyllithium reagents through structurally well-defined Ar—Cu(III) intermediates, Chem Commun, 48: 9418-9420 (2012). |
| Williams, E. et al., “Excimer□Based White Phosphorescent Organic Light□Emitting Diodes with Nearly 100 % Internal Quantum Efficiency”, Advanced Materials, Jan. 2007, vol. 19, No. 2, pp. 197-202 <DOI:10.1002/adma.200602174>. |
| Williams, E. et al., “Organic light-emitting diodes having exclusive near-infrared electrophosphorescence”, Applied Physics Letters, Aug. 2006, vol. 89, No. 8, pp. 083506-1-083506-3 <DOI:10.1063/1.2335275>. |
| Wong. Challenges in organometallic research—Great opportunity for solar cells and OLEDs. Journal of Organometallic Chemistry 2009, vol. 694, pp. 2644-2647. |
| Xiao-Chu Hang et al., “Highly Efficient Blue-Emitting Cyclometalated Platinum(II) Complexes by Judicious Molecular Design,” Angewandte Chemie, International Edition, vol. 52, Issue 26, Jun. 24, 2013, pp. 6753-6756. |
| Xiaofan Ren et al., “Ultrahigh Energy Gap Hosts in Deep Blue Organic Electrophosphorescent Devices,” Chem. Mater., vol. 16, 2004, pp. 4743-4747. |
| Xin Li et al., “Density functional theory study of photophysical properties of iridium (III) complexes with phenylisoquinoline and phenylpyridine ligands”, The Journal of Physical Chemistry C, 2011, vol. 115, No. 42, pp. 20722-20731. |
| Yakubov, L.A. et al., Synthesis and Properties of Zinc Complexes of mesoHexadecyloxy-Substituted Tetrabenzoporphyrin and Tetrabenzoazaporphyrins, Russian Journal of Organic Chemistry, 2008, vol. 44, No. 5, pp. 755-760. |
| Yang et al. (2005). “Nanoscale morphology of high-performance polymer solar cells,” Nano Lett., 5, 579-83. |
| Yang, X. et al., “Efficient Blue□ and White□Emitting Electrophosphorescent Devices Based on Platinum(II) [1,3□Difluoro□4,6□di(2□pyridinyl)benzene] Chloride”, Advanced Materials, Jun. 2008, vol. 20, No. 12, pp. 2405-2409 <DOI:10.1002/adma.200702940>. |
| Yao et al. (2008). “Effect of solvent mixture on nanoscale phase separation in polymer solar cells,” Adv. Funct. Mater., 18, 1783-89. |
| Yao et al., Cu(CI04)2-Mediated Arene C—H Bond Halogenations of Azacalixaromatics Using Alkali Metal Halides as Halogen Sources, The Journal of Organic Chemistry, 77(7): 3336-3340 (2012). |
| Ying Yang et al., “Induction of Circularly Polarized Electroluminescence from an Achiral Light-Emitting Polymer via a Chiral Small-Molecule Dopant,” Advanced Materials, vol. 25, Issue 18, May 14, 2013, pp. 2624-2628. |
| Yu et al. (1995). “Polymer Photovoltaic Cells: Enhanced efficiencies via a network of internal donor-acceptor heterojunctions,” Science, 270, 1789-91. |
| Z Liu et al., “Green and blue-green phosphorescent heteroleptic iridium complexes containing carbazole-functionalized beta-diketonate for non-doped organic light-emitting diodes”, Organic Electronics 9 (2008) pp. 171-182. |
| Z Xu et al., “Synthesis and properties of iridium complexes based 1,3,4-oxadiazoles derivatives”, Tetrahedron 64 (2008) pp. 1860-1867. |
| Zhi-Qiang Zhu et. al., “Efficient Cyclometalated Platinum(II) Complex with Superior Operational Stability,” Adv. Mater. 29 (2017) 1605002, pp. 1-5. |
| Zhi-Qiang Zhu et.al., “Harvesting All Electrogenerated Excitons through Metal Assisted Delayed Fluorescent Materials,” Adv. Mater. 27 (2015) 2533-2537. |
| Zhu, W. et al., “Highly efficient electrophosphorescent devices based on conjugated polymers doped with iridium complexes”, Applied Physics Letters, Mar. 2002, vol. 80, No. 12, pp. 2045-2047 <DOI:10.1063/1.1461418>. |
| Dong Ryun Lee et al. “Emitting Materials for Thermally Activated Delayed Fluorescent Organic Light-Emitting Diodes Using Benzofurocarbazole and Benzothienocarbazole as Donor Moieties” SID 2015 Digest, vol. 46, p. 502-504 (Year: 2015). |
| Fleetham et al., “Phosphorescent Pt(II) and Pd(II) Complexes for Efficient, High-Color-Quality, and Stable OLEDs”, Advanced Mater., 29, 1601861, 2017, 16 pages. |
| Tyler Fleetham, “Phosphorescent Pt(II) and Pd(II) Complexes for Efficient, High-Color-Quality, and Stable OLEDs”, 52 pages, Material Science and Engineering, Arizona State University (Year: 2016). |
| J. Park et al., 26 Semicond. Sci. Technol., 1-9 (2011) (Year: 2011). |
| S. Kunic et al., 54th International Symposium ELMAR—2012, 31-35 (2012) (Year: 2012). |
| T. Fleetham et al., 25 Advanced Materials, 2573-2576 (2013) (Year: 2013). |
| Y. Karzazi, 5 J. Mater. Environ. Sci., 1-12 (2014) (Year: 2014). |
| Myoung-Seon Gong et al. “Synthesis and device properties of mCP analogues based on fused-ring carbazole moiety”, Org. Electronics, 2017, vol. 42, p. 66-74 (Year: 2017). |
| Number | Date | Country | |
|---|---|---|---|
| 20210363420 A1 | Nov 2021 | US |
| Number | Date | Country | |
|---|---|---|---|
| 63026806 | May 2020 | US |
