Patent Application
20170174826
The present invention generally relates to compounds that may be used as building blocks to construct donor-acceptor polymers. More particularly, the present invention relates to electron-deficient imide-fused pyridazines and imide-fused phthalazines. The present invention also relates to the donor-acceptor polymers constructed using said building blocks and methods for preparing such building blocks and donor-acceptor polymers.
Organic electronics materials have attracted attention due to their potential in applications such as organic field effect transistors, organic light emitting diodes, organic photovoltaic cells, organic electrochromic materials and sensor materials. However, the commercialization of such devices have been slow due to the lack of suitable materials having high stability, long shelf-life, high performance and a low cost of production.
Donor-acceptor type conjugated oligomers and polymers have been investigated as organic electronics materials. The physical and optical properties of donor-acceptor type conjugated oligomers and polymers can be conveniently tuned by adjustment of their donor and acceptor moieties.
In many applications of organic electronics materials, the electron affinity of the acceptor building blocks is of great importance in tuning the physical and optical properties of the materials and in most cases is crucial to assure the required performance characteristics of the material. The electron affinity plays a vital role in controlling the band-gap of the resultant conjugated polymers. In order to make low band-gap conjugated polymers with desired absorption characteristics for opto-electronic applications, more electron-deficient acceptors especially with high electron deficiency are needed to manufacture organic electronics materials.
There is therefore a need to provide building blocks that overcome, or at least ameliorate, one or more of the disadvantages described above. There is also a need to provide donor-acceptor polymers produced by these building blocks, which may be used as organic electronics materials that overcome, or at least ameliorate, one or more of the disadvantages described above. There is also a need to provide a method of synthesizing building blocks and donor-acceptor polymers that overcome, or at least ameliorate, one or more of the disadvantages described above.
In a first aspect, there is provided a compound having the following Formula (I);
Advantageously, the compound of Formula (I) as defined above may combine an electron withdrawing imide group to an electron deficient pyridazine or phthalazine group, resulting in the compound having ultra-high electron affinity. The compound of Formula (I) as defined above may be used as electron-deficient acceptors with unprecedentedly high electron affinity. The compound of Formula (I) as defined above may be even more electron deficient compared to conventional compounds. Further advantageously, the compound of Formula (I) may be easy to functionalize, allowing for fine-tuning of not only its electronic properties but also to enhance its processability. For example, the compound of Formula (I) as defined above may be easily functionalized to improve its solubility. More advantageously, the easily functionalizable nature of the compound of Formula (I) may facilitate its integration with donor compounds. This may be useful, for example, in the manufacture of more processable polymers which may further be used as organic electronic materials.
In many applications of organic electronics materials, the electron affinity of the building blocks may be of great importance in tuning the physical and optical properties of the materials and in most cases may be crucial to ensure that the resulting material has the correct characteristics. The electron affinity may play a vital role in controlling the band-gap of the resultant conjugated polymers formed from the electron deficient pyridazine or phthalazine group. Advantageously, by attaching an electron withdrawing imide group to an electron deficient pyridazine or phthalazine group, a compound of Formula (I), which may possess ultra-high electron affinity, may be formed. This building block defined by Formula (I) may be designed to be easily functionalizable and therefore may be of high importance for the development of organic electronics materials. More advantageously, the compound of Formula (I) may be synthesized with a good overall synthetic yield. Further, the compound of Formula (I) may be easily incorporated into donor-acceptor conjugated polymers.
In a second aspect, there is provided a compound having repeating units of the following Formula (IV);
Advantageously, the compound of Formula (IV) may be a polymer. The purification of a polymer may be much easier and more convenient than purification of small molecules. Advantageously, the simple purification process may significantly reduce the cost of production of the polymer. Further advantageously, the polymer may have good solubility in a variety of solvents. The polymer may be soluble in non-chlorinated solvents, making the polymer easily processable in solution. This may further reduce the cost of production. More advantageously, the polymer may become glassy upon heating and this may be useful in manufacturing devices using the polymer material.
Further advantageously, the polymer may be a donor-acceptor polymer. Advantageously, the polymer may be comprised of donor compounds and acceptor compounds. Further advantageously, the donor compounds and acceptor compounds may be selected to confer advantageous properties to the polymer. Advantageously, the acceptor compound in the polymer may be the compound of Formula (I) as defined above. The ultra-electron deficient nature of the compound of Formula (I) as defined above may enable ease of synthesis of the polymer as well as confer advantageous properties to the polymer. Further advantageously, the pyridazine or phthalazine group of the compound of Formula (I) may lower the frontier orbitals of the polymers to make the polymer more stable under ambient conditions.
The performance of donor-acceptor type conjugated oligomers and polymers may rely on many factors, including the identity of the donor and acceptor building block of the polymer, the polymerization strategy and the molar weight of the polymer. Advantageously, the compound of Formula (IV) as defined above has been synthesized by judicious choice of the donor and acceptor building block, polymerization strategy and molecular weight of the polymer to so that the polymer has the advantageous properties such as good band-gap, good optical property, high stability and low cost of production.
In a third aspect, there is provided a compound having the following Formula (VI);
Advantageously, the compound of Formula (I) as defined above may be a useful starting material for the synthesis of compounds defined further below. Advantageously, the compound of Formula (I) as defined above may comprise a tetrazine moiety attached to two electron donating groups. Advantageously, the tetrazine moiety may be electron-rich, such that when reacted with a dienophile defined further below, the resulting product will have ultra-high electron affinity.
In a fourth aspect, there is provided a compound having the following formula (VIIa) or (VIIb);
Advantageously, the compounds of formula (VIIa) or (VIIb) as defined above may be intrinsically electron-withdrawing, such that when reacted with the tetrazine compound having Formula (VI) as defined above, the resulting product will have ultra-high electron affinity. Further advantageously, the compounds of Formula (VIIa) or (VIIb) may be easy to functionalize. More advantageously, the compound of Formula (VIIa) or (VIIb) as defined above may be tunable by their R2 functional group to enhance their solubility properties such that they may be useful in reactions performed in a variety of solvents.
In a fifth aspect, there is provided a method for synthesizing the compound of Formula (VI) as defined above, comprising the steps of providing a hydrazine and contacting the hydrazine with a functionalized cyclic group, wherein the cyclic group of the functionalized cyclic group is selected from the group comprising of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted tellurophene, optionally substituted pyrrole, optionally substituted phenylene, optionally substituted aza-phenylene, optionally substituted arylene diimide, optionally substituted fluorene, optionally substituted cabazole, optionally substituted dibenzodilole, optionally substituted benzooxodiazole, optionally substituted benzotriazole, optionally substituted benzothidiazole and any combination thereof.
In a sixth aspect, there is provided a method for synthesizing the compound of Formula (I) as defined above, comprising the steps of:
Advantageously, the method for synthesizing the compound of Formula (I) as defined above may be an inverse-electron demanding Diels-Alder reaction. Conventionally, for Diels-Alder reactions that are being carried out on a tetrazine, the tetrazine acts as a diene and therefore should be modified with electron withdrawing groups to enhance its reactivity. Conversely, the dienophile should be modified with electron donating groups. This is to facilitate the inverse electron demanding Diels-Alder reaction. However, in the synthesis of the compound of Formula (I) as defined above, the tetrazine moiety has two electron donating units PI attached. In addition, the dienophile (compounds of Formulae (VIIa) or (VIIb) as defined above) is an intrinsically electron withdrawing imide. Under such conditions, the inverse-electron demanding Diels-Alder reaction has conventionally faced challenges due to the unfavourable electronic interaction between the tetrazine and the dienophile.
However, advantageously, the compound of Formula (I) may be synthesized with a good overall yield by the method as defined above. More advantageously, the successful synthesis may be due to judicious choice of reaction solvents, reaction temperature and reaction duration. Advantageously, the solvent used for the reaction may not contain any reactivity towards the reaction mixture. More advantageously, the boiling point of the solvent may be sufficiently high to allow the reaction to proceed. Advantageously, the method as defined above may enable the synthesis of the compound of Formula (I) with an isolated yield of higher than 90%.
Further advantageously, the method as defined above is scalable. The compound of Formula (I) as defined above may therefore be synthesized at a larger scale of up to 500 g.
In an seventh aspect, there is provided a method for synthesizing the compound of Formula (IV) as defined above, comprising the step of:
In an eighth aspect, there is provided a method for synthesizing the compound of Formula (IV) as defined above, comprising the steps of:
Advantageously, the method as defined above may have a high yield of synthesis. Further advantageously, the method as defined above may facilitate a controlled polymerization of the monomers, giving rise to polymers with defined ratios of donors and acceptors.
In a ninth aspect, there is provided the use of the compound of Formula (IV) as defined above, in the manufacture of semiconductor devices.
In a tenth aspect, there is provided a semiconductor device comprising the compound of Formula (IV) as defined above.
Advantageously, the compound of Formula (IV) as defined above may be useful in the manufacture of semiconductor devices. More advantageously, the compound of Formula (IV) as defined above may have enhanced processability, enabling them to be used in the manufacture of more processable polymers. Advantageously, the semiconductor devices manufactured using the compound of Formula (IV) as defined above may be used in a wide range of applications such as electrochromic materials, organic light-emitting diode, organic thin-film transistors and organic photovoltaic cells. Advantageously, the semiconductor devices manufactured using the compound of Formula (IV) may have higher stability, long shelf-life, high performance and may be cheaper to manufacture. Further advantageously, the device comprising the compound of Formula (IV) as defined above may have improved optical properties.
In this specification a number of terms are used which are well known to a skilled addressee. Nevertheless for the purposes of clarity a number of terms will be defined. The following words and terms used herein shall have the meaning indicated:
In the definitions of a number of substituents below it is stated that “the group may be a terminal group or a bridging group”. This is intended to signify that the use of the term is intended to encompass the situation where the group is a linker between two other portions of the molecule as well as where it is a terminal moiety. Using the term alkyl as an example, some publications would use the term “alkylene” for a bridging group and hence in these other publications there is a distinction between the terms “alkyl” (terminal group) and “alkylene” (bridging group). In the present application no such distinction is made and most groups may be either a bridging group or a terminal group.
“Acyl” means an R—C(═O)— group in which the R group may be an alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl group as defined herein. Examples of acyl include acetyl and benzoyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the carbonyl carbon.
“Acylamino” means an R—C(═O)—NH— group in which the R group may be an alkyl, cycloalkyl, heterocycloalkyl; aryl or heteroaryl group as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
“Alkenyl” as a group or part of a group denotes an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be straight or branched preferably having 2-12 carbon atoms, more preferably 2-10 carbon atoms, most preferably 2-6 carbon atoms, in the normal chain. The group may contain a plurality of double bonds in the normal chain and the orientation about each is independently E or Z. Exemplary alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and nonenyl. The group may be a terminal group or a bridging group.
“Alkenyloxy” refers to an alkenyl-O— group in which alkenyl is as defined herein. Preferred alkenyloxy groups are C1-C6 alkenyloxy groups. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
“Alkyl” as a group or part of a group refers to a linear or branched aliphatic hydrocarbon group, preferably a C1-C25 alkyl, more preferably a C1-C10 alkyl, most preferably C1-C6 unless otherwise noted. Examples of suitable straight and branched C1-C6 alkyl substituents include methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, t-butyl, hexyl, and the like. The group may be a terminal group or a bridging group.
“Alkylamino” includes both mono-alkylamino and dialkylamino, unless specified. “Mono-alkylamino” means a Alkyl-NH— group, in which alkyl is as defined herein. “Dialkylamino” means a (alkyl)2N— group, in which each alkyl may be the same or different and are each as defined herein for alkyl. The alkyl group is preferably a C1-C6 alkyl group. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
“Alkylaminocarbonyl” refers to a group of the formula (Alkyl)x(H)yNC(═O)— in which alkyl is as defined herein, x is 1 or 2, and the sum of X+Y=2. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the carbonyl carbon.
“Alkyloxy” refers to an alkyl-O— group in which alkyl is as defined herein. Preferably the alkyloxy is a C1-C6alkyloxy. Examples include, but are not limited to, methoxy and ethoxy. The group may be a terminal group or a bridging group.
“Alkyloxyalkyl” refers to an alkyloxy-alkyl-group in which the alkyloxy and alkyl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
“Alkyloxyary” refers to an alkyloxy-aryl-group in which the alkyloxy and aryl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the aryl group.
“Alkyloxycarbonyl” refers to an alkyl-O—C(═O)— group in which alkyl is as defined herein. The alkyl group is preferably a C1-C6 alkyl group. Examples include, but are not limited to, methoxycarbonyl and ethoxycarbonyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the carbonyl carbon.
“Alkyloxycycloalkyl” refers to an alkyloxy-cycloalkyl-group in which the alkyloxy and cycloalkyl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the cycloalkyl group.
“Alkyloxyheteroaryl” refers to an alkyloxy-heteroaryl-group in which the alkyloxy and heteroaryl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heteroaryl group.
“Alkyloxyheterocycloalkyl” refers to an alkyloxy-heterocycloalkyl-group in which the alkyloxy and heterocycloalkyl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heterocycloalkyl group.
“Alkylsulfinyl” means an alkyl-S—(═O)— group in which alkyl is as defined herein. The alkyl group is preferably a C1-C6 alkyl group. Exemplary alkylsulfinyl groups include, but not limited to, methylsulfinyl and ethylsulfinyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
“Alkylsulfonyl” refers to an alkyl-S(═O)2— group in which alkyl is as defined above. The alkyl group is preferably a C1-C6 alkyl group. Examples include, but not limited to methylsulfonyl and ethylsulfonyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
“Alkynyl” as a group or part of a group means an aliphatic hydrocarbon group containing a carbon-carbon triple bond and which may be straight or branched preferably having from 2-12 carbon atoms, more preferably 2-10 carbon atoms, more preferably 2-6 carbon atoms in the normal chain. Exemplary structures include, but are not limited to, ethynyl and propynyl. The group may be a terminal group or a bridging group.
“Alkynyloxy” refers to an alkynyl-O— group in which alkynyl is as defined herein. Preferred alkynyloxy groups are C1-C6 alkynyloxy groups. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
“Amino” refers to groups of the form —NRaRb wherein Ra and Rb are individually selected from the group including but not limited to hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, and optionally substituted aryl groups.
“Aminoalkyl” means an NH2-alkyl-group in which the alkyl group is as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
“Aminosulfonyl” means an NH2—S(═O)2— group. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
“Aryl” as a group or part of a group denotes (i) an optionally substituted monocyclic, or fused polycyclic, aromatic carbocycle (ring structure having ring atoms that are all carbon) preferably having from 5 to 18 atoms per ring. Examples of aryl groups include phenyl, naphthyl, and the like; (ii) an optionally substituted partially saturated bicyclic aromatic carbocyclic moiety in which a phenyl and a C5-7 cycloalkyl or C5-7 cycloalkenyl group are fused together to form a cyclic structure, such as tetrahydronaphthyl, indenyl or indanyl. The group may be a terminal group or a bridging group. Typically an aryl group is a C3-C18 aryl group.
“Arylalkenyl” means an aryl-alkenyl-group in which the aryl and alkenyl are as defined herein. Exemplary arylalkenyl groups include phenylallyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkenyl group.
“Arylalkyl” means an aryl-alkyl-group in which the aryl and alkyl moieties are as defined herein. Preferred arylalkyl groups contain a C1-5 alkyl moiety. Exemplary arylalkyl groups include benzyl, phenethyl, 1-naphthalenemethyl and 2-naphthalenemethyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
“Arylalkyloxy” refers to an aryl-alkyl-O— group in which the alkyl and aryl are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
“Arylamino” includes both mono-arylamino and di-arylamino unless specified. Mono-arylamino means a group of formula arylNH—, in which aryl is as defined herein, di-arylamino means a group of formula (aryl)2N— where each aryl may be the same or different and are each as defined herein for aryl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
“Arylheteroalkyl” means an aryl-heteroalkyl-group in which the aryl and heteroalkyl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heteroalkyl group.
“Aryloxy” refers to an aryl-O— group in which the aryl is as defined herein. Preferably the aryloxy is a C6-C18aryloxy, more preferably a C6-C10 aryloxy. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
“Arylsulfonyl” means an aryl-S(═O)2— group in which the aryl group is as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
A “bond” is a linkage between atoms in a compound or molecule. The bond may be a single bond, a double bond, or a triple bond.
“Cycloalkenyl” means a non-aromatic monocyclic or multicyclic ring system containing at least one carbon-carbon double bond and preferably having from 5-10 carbon atoms per ring. Exemplary monocyclic cycloalkenyl rings include cyclopentenyl, cyclohexenyl or cycloheptenyl. The cycloalkenyl group may be substituted by one or more substituent groups. A cycloalkenyl group typically is a C3-C12 alkenyl group. The group may be a terminal group or a bridging group.
“Cycloalkyl” refers to a saturated monocyclic or fused or spiro polycyclic, carbocycle preferably containing from 3 to 9 carbons per ring, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, unless otherwise specified. It includes monocyclic systems such as cyclopropyl and cyclohexyl, bicyclic systems such as decalin, and polycyclic systems such as adamantane. A cycloalkyl group typically is a C3-C12 alkyl group. The group may be a terminal group or a bridging group.
“Cycloalkylalkyl” means a cycloalkyl-alkyl-group in which the cycloalkyl and alkyl moieties are as defined herein. Exemplary monocycloalkylalkyl groups include cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl and cycloheptylmethyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
“Cycloalkylalkenyl” means a cycloalkyl-alkenyl-group in which the cycloalkyl and alkenyl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkenyl group.
“Cycloalkylheteroalkyl” means a cycloalkyl-heteroalkyl-group in which the cycloalkyl and heteroalkyl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heteroalkyl group.
“Cycloalkyloxy” refers to a cycloalkyl-O— group in which cycloalkyl is as defined herein. Preferably the cycloalkyloxy is a C1-C6cycloalkyloxy. Examples include, but are not limited to, cyclopropanoxy and cyclobutanoxy. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
“Cycloalkenyloxy” refers to a cycloalkenyl-O— group in which the cycloalkenyl is as defined herein. Preferably the cycloalkenyloxy is a C1-C6cycloalkenyloxy. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
“Cycloamino” refers to a saturated monocyclic, bicyclic, or polycyclic ring containing at least one nitrogen in at least one ring. Each ring is preferably from 3 to 10 membered, more preferably 4 to 7 membered. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
“Haloalkyl” refers to an alkyl group as defined herein in which one or more of the hydrogen atoms has been replaced with a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine. A haloalkyl group typically has the formula CnH(2n+1−m)Xm wherein each X is independently selected from the group consisting of F, Cl, Br and I. In groups of this type n is typically from 1 to 10, more preferably from 1 to 6, most preferably 1 to 3. m is typically 1 to 6, more preferably 1 to 3. Examples of haloalkyl include fluoromethyl, difluoromethyl and trifluoromethyl.
“Haloalkenyl” refers to an alkenyl group as defined herein in which one or more of the hydrogen atoms has been replaced with a halogen atom independently selected from the group consisting of F, Cl, Br and I.
“Haloalkynyl” refers to an alkynyl group as defined herein in which one or more of the hydrogen atoms has been replaced with a halogen atom independently selected from the group consisting of F, Cl, Br and I.
“Halogen” represents chlorine, fluorine, bromine or iodine.
“Heteroalkyl” refers to a straight- or branched-chain alkyl group preferably having from 2 to 12 carbons, more preferably 2 to 6 carbons in the chain, one or more of which has been replaced by a heteroatom selected from S, O, P and N. Exemplary heteroalkyls include alkyl ethers, secondary and tertiary alkyl amines, amides, alkyl sulfides, and the like. Examples of heteroalkyl also include hydroxyC1-C5alkyl, C1-C6alkyloxyC1-C6alkyl, aminoC1-C6alkyl, C1-C6alkylaminoC1-C6alkyl, and di(C1-C6alkyl)aminoC1-C6alkyl. The group may be a terminal group or a bridging group.
“Heteroalkyloxy” refers to an heteroalkyl-O— group in which heteroalkyl is as defined herein. Preferably the heteroalkyloxy is a C1-C6heteroalkyloxy. The group may be a terminal group or a bridging group.
“Heteroaryl” either alone or part of a group refers to groups containing an aromatic ring (preferably a 5 or 6 membered aromatic ring) having one or more heteroatoms as ring atoms in the aromatic ring with the remainder of the ring atoms being carbon atoms. Suitable heteroatoms include nitrogen, oxygen and sulphur. Examples of heteroaryl include thiophene, benzothiophene, benzofuran, benzimidazole, benzoxazole, benzothiazole, benzisothiazole, naphtho[2,3-b]thiophene, furan, isoindolizine, xantholene, phenoxatine, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, tetrazole, indole, isoindole, 1H-indazole, purine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, cinnoline, carbazole, phenanthridine, acridine, phenazine, thiazole, isothiazole, phenothiazine, oxazole, isooxazole, furazane, phenoxazine, 2-, 3- or 4-pyridyl, 2-, 3-, 4-, 5-, or 8-quinolyl, 1-, 3-, 4-, or 5-isoquinolinyl 1-, 2-, or 3-indolyl, and 2-, or 3-thienyl. A heteroaryl group is typically a C1-C18 heteroaryl group. The group may be a terminal group or a bridging group. Typically a heteroaryl group is a 3 to 18 membered group.
“Heteroarylalkyl” means a heteroaryl-alkyl group in which the heteroaryl and alkyl moieties are as defined herein. Preferred heteroarylalkyl groups contain a lower alkyl moiety. Exemplary heteroarylalkyl groups include pyridylmethyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
“Heteroarylalkenyl” means a heteroaryl-alkenyl-group in which the heteroaryl and alkenyl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkenyl group.
“Heteroarylheteroalkyl” means a heteroaryl-heteroalkyl-group in which the heteroaryl and heteroalkyl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heteroalkyl group.
“Heteroarylamino” refers to groups containing an aromatic ring (preferably 5 or 6 membered aromatic ring) having at least one nitrogen and at least another heteroatom as ring atoms in the aromatic ring, preferably from 1 to 3 heteroatoms in at least one ring. Suitable heteroatoms include nitrogen, oxygen and sulphur. Arylamino and aryl is as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
“Heteroaryloxy” refers to a heteroaryl-O— group in which the heteroaryl is as defined herein. Preferably the heteroaryloxy is a C1-C18heteroaryloxy. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
“Heterocyclic” refers to saturated, partially unsaturated or fully unsaturated monocyclic, bicyclic or polycyclic ring system containing at least one heteroatom selected from the group consisting of nitrogen, sulfur and oxygen as a ring atom. Examples of heterocyclic moieties include heterocycloalkyl, heterocycloalkenyl and heteroaryl.
“Heterocycloalkenyl” refers to a heterocycloalkyl as defined herein but containing at least one double bond. A heterocycloalkenyl group typically is a C2-C12 heterocycloalkenyl group. The group may be a terminal group or a bridging group.
“Heterocycloalkyl” refers to a saturated monocyclic, bicyclic, or polycyclic ring containing at least one heteroatom selected from nitrogen, sulfur, oxygen, preferably from 1 to 3 heteroatoms in at least one ring. Each ring is preferably from 3 to 10 membered, more preferably 4 to 7 membered. Examples of suitable heterocycloalkyl substituents include pyrrolidyl, tetrahydrofuryl, tetrahydrothiofuranyl, piperidyl, piperazyl, tetrahydropyranyl, morphilino, 1,3-diazapane, 1,4-diazapane, 1,4-oxazepane, and 1,4-oxathiapane. A heterocycloalkyl group typically is a C2-C12 heterocycloalkyl group. The group may be a terminal group or a bridging group.
“Heterocycloalkylalkyl” refers to a heterocycloalkyl-alkyl-group in which the heterocycloalkyl and alkyl moieties are as defined herein. Exemplary heterocycloalkylalkyl groups include (2-tetrahydrofuryl)methyl, (2-tetrahydrothiofuranyl) methyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
“Heterocycloalkylalkenyl” refers to a heterocycloalkyl-alkenyl-group in which the heterocycloalkyl and alkenyl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkenyl group.
“Heterocycloalkylheteroalkyl” means a heterocycloalkyl-heteroalkyl-group in which the heterocycloalkyl and heteroalkyl moieties are as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heteroalkyl group.
“Heterocycloalkyloxy” refers to a heterocycloalkyl-O— group in which the heterocycloalkyl is as defined herein. Preferably the heterocycloalkyloxy is a C1-C6heterocycloalkyloxy. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
“Heterocycloalkenyloxy” refers to a heterocycloalkenyl-O— group in which heterocycloalkenyl is as defined herein. Preferably the Heterocycloalkenyloxy is a C1-C6 Heterocycloalkenyloxy. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
“Heterocycloamino” refers to a saturated monocyclic, bicyclic, or polycyclic ring containing at least one nitrogen and at least another heteroatom selected from nitrogen, sulfur, oxygen, preferably from 1 to 3 heteroatoms in at least one ring. Each ring is preferably from 3 to 10 membered, more preferably 4 to 7 membered. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
“Hydroxyalkyl” refers to an alkyl group as defined herein in which one or more of the hydrogen atoms has been replaced with an OH group. A hydroxyalkyl group typically has the formula CnH(2n+1−x)(OH)x. In groups of this type n is typically from 1 to 10, more preferably from 1 to 6, most preferably from 1 to 3. x is typically from 1 to 6, more preferably from 1 to 4.
“Lower alkyl” as a group means unless otherwise specified, an aliphatic hydrocarbon group which may be straight or branched having 1 to 6 carbon atoms in the chain, more preferably 1 to 4 carbons such as methyl, ethyl, propyl (n-propyl or isopropyl) or butyl (n-butyl, isobutyl or tertiary-butyl). The group may be a terminal group or a bridging group.
“Subject” refers to a human or an animal.
“Sulfinyl” means an R—S(═O)— group in which the R group may be OH, alkyl, cycloalkyl, heterocycloalkyl; aryl or heteroaryl group as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
“Sulfinylamino” means an R—S(═O)—NH— group in which the R group may be OH, alkyl, cycloalkyl, heterocycloalkyl; aryl or heteroaryl group as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
“Sulfonyl” means an R—S(═O)2— group in which the R group may be OH, alkyl, cycloalkyl, heterocycloalkyl; aryl or heteroaryl group as defined herein. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
“Sulfonylamino” means an R—S(═O)2—NH— group. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
It is understood that included in the family of compounds of Formula (I) are isomeric forms including diastereoisomers, enantiomers, tautomers, and geometrical isomers in “E” or “Z” configurational isomer or a mixture of E and Z isomers. It is also understood that some isomeric forms such as diastereomers, enantiomers, and geometrical isomers can be separated by physical and/or chemical methods and by those skilled in the art.
Some of the compounds of the disclosed embodiments may exist as single stereoisomers, racemates, and/or mixtures of enantiomers and/or diastereomers. All such single stereoisomers, racemates and mixtures thereof, are intended to be within the scope of the subject matter described and claimed.
Additionally, Formula (I) is intended to cover, where applicable, solvated as well as unsolvated forms of the compounds. Thus, each formula includes compounds having the indicated structure, including the hydrated as well as the non-hydrated forms.
Further, it is possible that compounds of the invention may contain more than one asymmetric carbon atom. In those compounds, the use of a solid line to depict bonds to asymmetric carbon atoms is meant to indicate that all possible stereoisomers are meant to be included. The use of a solid line to depict bonds to one or more asymmetric carbon atoms in a compound of the invention and the use of a solid or dotted wedge to depict bonds to other asymmetric carbon atoms in the same compound is meant to indicate that a mixture of diastereomers is present.
The term “optionally substituted” as used herein means the group to which this term refers may be unsubstituted, or may be substituted with one or more groups independently selected from alkyl, alkenyl, alkynyl, thioalkyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkylalkenyl, heterocycloalkyl, cycloalkylheteroalkyl, cycloalkyloxy, cycloalkenyloxy, cycloamino, halo, carboxyl, haloalkyl, haloalkynyl, alkynyloxy, heteroalkyl, heteroalkyloxy, hydroxyl, hydroxyalkyl, alkoxy, thioalkoxy, alkenyloxy, haloalkoxy, haloalkenyl, haloalkynyl, haloalkenyloxy, nitro, amino, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroheterocyclyl, alkylamino, dialkylamino, alkenylamine, aminoalkyl, alkynylamino, acyl, alkyloxy, alkyloxyalkyl, alkyloxyaryl, alkyloxycarbonyl, alkyloxycycloalkyl, alkyloxyheteroaryl, alkyloxyheterocycloalkyl, alkenoyl, alkynoyl, acylamino, diacylamino, acyloxy, alkylsulfonyloxy, heterocyclic, heterocycloalkenyl, heterocycloalkyl, heterocycloalkylalkyl, heterocycloalkylalkenyl, heterocycloalkylheteroalkyl, heterocycloalkyloxy, heterocycloalkenyloxy, heterocycloxy, heterocycloamino, haloheterocycloalkyl, alkylsulfinyl, alkylsulfonyl, alkylsulfenyl, alkylcarbonyloxy, alkylthio, acylthio, aminosulfonyl, phosphorus-containing groups such as phosphono and phosphinyl, sulfinyl, sulfinylamino, sulfonyl, sulfonylamino, aryl, heteroaryl, heteroarylalkyl, heteroarylalkenyl, heteroarylheteroalkyl, heteroarylamino, heteroaryloxy, arylalkenyl, arylalkyl, alkylaryl, alkylheteroaryl, aryloxy, arylsulfonyl, cyano, cyanate, isocyanate, —C(O)NH(alkyl), and —C(O)N(alkyl)2.
The term “optionally substituted alkyl”, for the purpose of this this application, refers to an optionally substituted linear alkyl or an optionally substituted branched alkyl. The optionally substituted linear alkyl may be an optionally substituted C1 to C25 linear alkyl. The optionally substituted branched alkyl may be an optionally substituted C1 to C25 branched alkyl. The optionally substituted branched alkyl may have the following formula (A), where h may be 0 or 1. i and j may independently be integers selected from 1 to 13. h may be 1. i may be 7. j may be 9.
The word “substantially” does not exclude “completely” e.g. a composition which is “substantially free” from Y may be completely free from Y. Where necessary, the word “substantially” may be omitted from the definition of the invention.
Unless specified otherwise, the terms “comprising” and “comprise”, and grammatical variants thereof, are intended to represent “open” or “inclusive” language such that they include recited elements but also permit inclusion of additional, unrecited elements.
As used herein, the term “about”, in the context of concentrations of components of the formulations, typically means +/−5% of the stated value, more typically +/−4% of the stated value, more typically +/−3% of the stated value, more typically, +/−2% of the stated value, even more typically +/−1% of the stated value, and even more typically +/−0.5% of the stated value.
Throughout this disclosure, certain embodiments may be disclosed 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 disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges 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 sub-ranges 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, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
Certain embodiments may also be described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the disclosure. This includes the generic description of the embodiments with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.
The accompanying drawings illustrate a disclosed embodiment and serves to explain the principles of the disclosed embodiment. It is to be understood, however, that the drawings are designed for purposes of illustration only, and not as a definition of the limits of the invention.
A compound may have the following Formula (I);
A compound may have repeating units of the following Formula (IV);
A compound may have repeating units of the following formula (IVa) or (IVb):
A compound may have the following Formula (VI);
A compound may have the following formula (VIIa) or (VIIb);
P1 may have the following Formula (IIa) or (IIb);
P2 may have the following formula (IIIa) or (IIIb);
P3 has the following Formula (Va), (Vb) or (Vc);
P4 may be absent, or an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl.
may be a single or double bond, as valency allows.
m may be 0 or 1.
n may be an integer selected from 1 to 4.
X, X1, X2, X3, X4 and X5 may independently be absent or selected from the group consisting of a bond, H, halogen, CN, R1, OR1 or SR1.
Halogen may be selected from the group consisting of F, Cl, Br and I.
X may be selected from the group consisting of halogen, CN, R1 and OR1.
R1 may be selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl. R1 may be an optionally substituted alkyl.
A1 may be selected from the group consisting of O, S, Se, Te, C and N.
A2, A3, A4, A5 and A6 may independently be C or N.
Any two substituents selected from the group consisting of X1, X2, X3, X4 and X5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl.
R2 may be an optionally substituted alkyl or optionally substituted aryl.
X7 may be O or S.
A7 may be CH, CH2 or N.
may be where the compound of Formula (IIIa) or (IIIb) is fused to the compound of Formula (I) of Formula (IV).
q may be 0 or 1.
t may be an integer selected from 1 to 4.
X8, X9, X11 and X12 may independently be absent or selected from the group consisting of a bond, H, halogen, CN, R3, OR3 or SR3.
R3 may be selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl.
A8 may be selected from the group consisting of O, S, Se, Te, C and N.
A9, A10, A11, A12 and A13 may independently be C or N.
Any two substituents selected from the group consisting of X8, X9, X10, X11 and X12 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl.
a may be any value from 0 to 1.
b may be an integer selected from 1 to 10,000.
y may be an integer selected from 0 to 5.
Optionally substituted alkyl may be an optionally substituted C1-C25 alkyl, optionally substituted alkenyl may be an optionally substituted C2-C2s alkenyl, optionally substituted alkynyl may be an optionally substituted C2-C25 alkynyl, optionally substituted cycloalkyl may be an optionally substituted C3-C12 cycloalkyl, optionally substituted heterocycloalkyl may be an optionally substituted C3-C12 heterocycloalkyl, optionally substituted cycloalkenyl may be an optionally substituted C3-C12 cycloalkenyl, optionally substituted heterocycloalkenyl may be an optionally substituted C3-C12 heterocycloalkenyl, optionally substituted aryl may be an optionally substituted C3-C18 aryl and optionally substituted heteroaryl may be an optionally substituted C3-C18 heteroaryl.
Optionally substituted heterocycloalkyl and optionally substituted heteroaryl may independently be a 3- to 18-membered monocyclic, bicyclic, or polycyclic ring.
P1
P1 may be selected from the group consisting of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted tellurophene, optionally substituted pyrrole, optionally substituted phenylene, optionally substituted aza-phenylene, optionally substituted arylene diimide, optionally substituted fluorene, optionally substituted cabazole, optionally substituted dibenzodilole, optionally substituted benzooxodiazole, optionally substituted benzotriazole, optionally substituted benzothidiazole and any combination thereof.
The P1 may have the following Formula (IIa);
A1 may be N. A1 may be S.
A3, A4, A5 and A6 may be C.
X1 may be H. X1 may be absent.
X4 and X5 may independently be selected from the group consisting of H, R1 and OR1. R1 may be an optionally substituted alkyl. X4 and X5 may be H.
X may be Br.
When m is 0, A1 may be N, and X1 may be H or optionally substituted alkyl.
When m is 0, A3, A4, A5 and A6 may be C, and X4 and X5 are independently selected from the group consisting of H, R1 and OR1, wherein R1 is optionally substituted alkyl.
When m is 0, A1 may be S; X1 may be absent; A3, A4, A5 and A6 may be C, X4 and X5 may be H and X may be Br,
When m is 0, A1 may be O; X1 may be absent; A3, A4, A5 and A6 may be C, X4 and X5 may be H and X may be Br.
The compound may have the following formula (VIIIa) or (VIIIb):
m may be 1.
A1, A2 A3, A4, A5 and A6 may be C. A1, A2 A3 and A6 may be C. A3 and A6 may be C. A4 and A5 may be N. A4 and A5 may be C.
X1, X2, X4 and X6 may independently be absent or selected from the group consisting of H, halogen, R1 and OR1. X1, X2, X4 and X6 may independently be H or halogen. X4 and X5 may independently be H or F.
R1 may be an optionally substituted alkyl.
X1and X2 may be taken together to form an optionally substituted 5-membered heteroaryl.
When m is 1, A3 and A6 may be C and X1, X2, X4 and X6 may be independently absent or selected from the group consisting of H, halogen, R1 and OR1, wherein R1 is optionally substituted alkyl.
When m is 1, A1, A2 A3, A4, A5 and A6 may be C and X1, X2, X4 and X6 may independently be H or halogen.
When m is 1, A1, A2 A3, A4, A5 and A6 may be C and X1, X2, X4 and X6 may be H.
The compound may have the following Formula (VIIIc):
When m is 1, A1, A2 A3 and A6 may be C and X1 and X2 may be taken together to form an optionally substituted 5-membered heteroaryl.
P1 may have the following formula (IX);
A14 may be selected from the group consisting of O, S, Se, Te and N.
X14 may be absent or optionally substituted alkyl.
When P1 has the formula (IX), A4 and A5 may be N.
When P1 has the formula (IX), A4 and A5 may be C; and X4 and X5 may independently be H or F.
P1 may have the following Formula (IIb);
A1, A2 A3, A4, A5 and A6 may be C.
X1, X4 and X5 may be H.
X2 and X3 may be taken together to form an optionally substituted 5-membered heterocycloalkyl. X2 and X3 may be taken together to form an optionally substituted 6-membered heterocycloalkyl. X3 and X4 may be taken together to form an optionally substituted a 6-membered aryl. X4 and X5 may be taken together to form an optionally substituted 6-membered heterocycloalkyl.
The optionally substituted 5-membered heterocycloalkyl may be further fused with an optionally substituted 6-membered aryl.
P1 may have the following formula (X);
A15 may be selected from the group consisting of NH, C(R4)2, and Si(R4)2. R4 may be an optionally substituted alkyl.
P1 may have the following Formula (XI);
X1, X15 and X16 may independently be selected from the group consisting of H, halogen and CN.
R6 and R7 may independently be selected from the group consisting of H, R8 and OR8, wherein R8 is optionally substituted alkyl.
u may be 1 or 2.
P2
P2 may be selected from the group consisting of optionally substituted imide and optionally substituted phthalamide.
R2 may be an optionally substituted alkyl. The optionally substituted alkyl may be an optionally substituted linear alkyl or an optionally substituted branched alkyl. The optionally substituted linear alkyl may be an optionally substituted C1 to C25 linear alkyl. The optionally substituted branched alkyl may be an optionally substituted C1 to C25 branched alkyl. The optionally substituted branched alkyl may have the following formula (XII).
N of Formula (XII) may be where the R2 group is connected to the rest of the compound in Formulae (IVa), (IVb), (IVc), (IVd), (VIIa) or (VIIb).
h may be 0 or 1. i and j may independently be integers selected from 1 to 13. h may be 1. i may be 7. j may be 9.
The optionally substituted alkyl may be 2-ethylheptyl, 2-heptylhexadecyl, 2-heptylpentadecyl, 2-heptyltetradecyl, 2-heptyltridecyl, 2-heptyldodeclyl, 2-heptylundecyl, 2-heptyldecyl, 2-heptylnonyl, 2-heptyloctyl, 2-heptylheptyl, 2-octylhexadecyl, 2-octylpentadecyl, 2-octyltetradecyl, 2-octyltridecyl, 2-octyldodecyl, 2-octylundecyl, 2-octyldecyl, 2-octylnonyl, 2-octyloctyl, 2-nonyltetradecyl, 2-nonyltridecyl, 2-nonyldodecyl, 2-nonylundecyl, 2-nonyldecyl or 2-nonylnonyl.
The optionally substituted may be any linear or branched alkyl chain that may confer improved solubility and processability of the final product.
X7 may be O.
R2 may be an optionally substituted aryl having the following Formula (XIII);
A16a, A16b, A16c, A16d and A16e may independently be selected from the group consisting of N, CH and CR9, wherein R9 is an optionally substituted alkyl. A16a may be N and A16b, A16c, A16d and A16e may be CH. A16b may be N and A16a, A16c, A16d, A16e may be CH. A16c may be N and A16a, A16b, A16d and A16e may be CH. A16b and A16d may be N and A16a, A16c, A16d and A16e may be CH. A16a, A16c, A16e may be N and A16b and A16d may be CH.
A7 may be CH. A7 may be CH2.
P2 may have the following formula (IIIa), (IIIb), (IIIc), or (IIId):
The compound may have the following formula (XIV), (XVa) or (XVb):
The compound of Formula (I) may be 6-alkyl-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (PPD). PPD may lower the frontier orbitals of the polymers to make the polymer more stable under ambient conditions.
P3
P3 may be a moiety that performs as a good electron donor in electrochromic materials. The chemical and physical nature of the P3 group may enhance the solubility and processability of the final polymer materials as well as the performance of the polymer films under voltage bias.
P3 may be selected from the group consisting of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted pyrrole, optionally substituted phenyl, optionally substituted fluorenes, optionally substituted carbazoles, optionally substituted fused furans and optionally substituted fused thiophenes.
P3 may have the following formula (Va);
q may be 0.
A8 may be N. A8 may be S. A10, A11, A12 and A13 may be C.
X8 may be H or an optionally substituted alkyl. X8 may be absent. X11 and X12 may independently be selected from the group consisting of H, R3 and OR3. R3 may be optionally substituted alkyl.
X11 and X12 may be taken together to form an optionally substituted 7-membered heterocycloalkyl.
When q is 0, A8 may be N, A10, A11, A12 and A13 may be C, Xs may be H and X11 and X12 may independently be selected from the group consisting of H, R3 and OR3, wherein R3 is optionally substituted alkyl.
When q is 0, A8 may be S; X8may be absent; A10, A11, A12 and A13 may be C and X may be Br.
When q is 0, A8 may be S; X8 may be absent; A10, A11, A12 and A13 may be C, and X11 and X12 may be taken together to form an optionally substituted 7-membered heterocycloalkyl. The optionally substituted 7-membered heterocycloalkyl may be substituted with two alkoxy groups. The alkoxy group may be OC12H25.
q may be 1.
A8, A9 A10, A11, A12 and A13 may be C. A10 and A13 may be C.
X8, X9, X11 and X12 may independently be selected from the group consisting of H, halogen, R3 and OR3. R3 may be an optionally substituted alkyl. X8, X9, X11 and X12 may be independently selected from the group consisting of H, halogen, OR10 and SR10. R10 may be an optionally substituted alkyl.
When q is 1, A10 and A13 may be C; X8, X9, X11 and X12 may independently be selected from the group consisting of H, halogen, R3 and OR3, wherein R3 may be optionally substituted alkyl.
When q is 1, A8, A9 A10, A11, A12 and A13 may be C and X8, X9, X11 and X12 may independently be selected from the group consisting of H, halogen, OR10 and SR10, wherein R10 may be an optionally substituted alkyl.
P3 may be a 3,4-dialkoxythiophene.
P3 may have the following Formula (XVI);
P3 may have the following formula (Vb);
A8, A9 A10, A11, A12 and A13 may be C.
X8, X11 and X12 may be H.
X9 and X10 may be taken together to form an optionally substituted 5-membered heterocycloalkyl.
The optionally substituted 5-membered heterocycloalkyl may be further fused with an optionally substituted 6-membered aryl.
P3 may have the following formula (XVII);
A17 may be selected from the group consisting of NH, C(R11)2, and Si(R11)2. R11 may be optionally substituted alkyl. R11 may be C8H17.
P3 may have the following Formula (Vc);
A10, A11, A12 and A13 may be C. X8 and X12 may be H.
X10 and X11 may be taken together to form an optionally substituted 5-membered heteroaryl. X10 and X11 may be taken together to form an optionally substituted 6-membered aryl. The optionally substituted 6-membered aryl may be further fused with an optionally substituted 5-membered heteroaryl.
P3 may have the following Formula (XVIIIa) or (XVIIIb);
A8 and A18 may be independently selected from the group consisting of O, S and Se.
P3 may have the following Formula (XIX);
A8 and A19 may independently be selected from the group consisting of O, Se and Se. R12 and R13 may independently be selected from the group consisting of R14, OR14 and SR14. R14 may be optionally substituted alkyl or optionally substituted aryl. R14 may be an optionally substituted alkyl. R14 may be C8H17. R14 may be a 2-ethylheptyl group.
P4
P4 may be absent, or selected from the group consisting of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted pyrrole, optionally substituted phenyl, optionally substituted fluorenes, optionally substituted carbazoles, optionally substituted fused furans and optionally substituted fused thiophenes.
P4 may have the following formula (Va);
q may be 0.
A8 may be N. A8 may be S. A10, A11, A12 and A13 may be C.
X8 may be H or an optionally substituted alkyl. X8 may be absent. X11 and X12 may independently be selected from the group consisting of H, R3 and OR3. R3 may be optionally substituted alkyl.
X11 and X12 may be taken together to form an optionally substituted 7-membered heterocycloalkyl.
When q is 0, A8 may be N, A10, A11, A12 and A13 may be C, X8 may be H and X11 and X12 may independently be selected from the group consisting of H, R3 and OR3, wherein R3 is optionally substituted alkyl.
When q is 0, A8 may be S; X8 may be absent and A10, A11, A12 and A13 may be C.
When q is 0, A8 may be S; X8 may be absent; A10, A11, A12 and A13 may be C and X11 and X12 may be taken together to form an optionally substituted 7-membered heterocycloalkyl. The optionally substituted 7-membered heterocycloalkyl may be substituted with two alkoxy groups. The alkoxy groups may be OC12H25.
q may be 1.
A8, A9 A10, A11, A12 and A13 may be C. A10 and A13 may be C.
X8, X9, X11 and X12 may independently be selected from the group consisting of H, halogen, R3 and OR3. R3 may be an optionally substituted alkyl. X8, X9, X11 and X12 may be independently selected from the group consisting of H, halogen, OR10 and SR10. R10 may be an optionally substituted alkyl.
When q is 1, A10 and A13 may be C; X8, X9, X11 and X12 may independently be selected from the group consisting of H, halogen, R3 and OR3, wherein R3 may be optionally substituted alkyl.
When q is 1, A8, A9 A10, A11, A12 and A13 may be C and X8, X9, X11 and X12 may independently be selected from the group consisting of H, halogen, OR10 and SR10, wherein R10 may be an optionally substituted alkyl.
P4 may have the following formula (Vb);
A8, A9 A10, A11, A12 and A13 may be C.
X8, X11 and X12 may be H.
X9 and X10 may be taken together to form an optionally substituted 5-membered heterocycloalkyl.
The optionally substituted 5-membered heterocycloalkyl may be further fused with an optionally substituted 6-membered aryl.
P4 may have the following formula (XVII);
A17 may be selected from the group consisting of NH, CHR11, C(R11)2, SiHR11 and Si(R11)2. R11 may be optionally substituted alkyl. R11 may be C8H17 or C12H25.
P4 may have the following Formula (Vc);
A10, A11, A12 and A13 may be C. X8 and X12 may be H.
X10 and X11 may be taken together to form an optionally substituted 5-membered heteroaryl. X10 and X11 may be taken together to form an optionally substituted 6-membered aryl. The optionally substituted 6-membered aryl may be further fused with an optionally substituted 5-membered heteroaryl.
P4 may have the following Formula (XVIIIa) or (XVIIIb);
A8 and A18 may be independently selected from the group consisting of O, S and Se.
P4 may have the following Formula (XIX);
A8 and A19 may independently be selected from the group consisting of O, Se and Se. R12 and R13 may independently be selected from the group consisting of R14, OR14 and SR14. R14 may be optionally substituted alkyl or optionally substituted aryl. R14 may be an optionally substituted alkyl.
P4 may be an optionally substituted thiophene or an optionally substituted fused thiophene.
P4 may have the following Formula (XXXIa) or (XXXIb):
a may be 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2 or 0.1. a may be 0.5, 0.3 or 0.1.
b may be an integer selected from 1 to 50, 1 to 10, 1 to 20, 1 to 30, 1 to 40, 10 to 20, 10 to 30, 10 to 40, 10 to 50, 20 to 30, 20 to 40, 20 to 50, 30 to 40, 30 to 50 or 40 to 50.
y may be 1. y may be 2.
The compound may have the following formula (XX):
The compound may have the following formula (XXa), (XXb) or (XXc):
The compound may have the following formula (XXI):
The compound may have the following formula (XXIa):
The compound may have the following formula (XXII):
The compound may have the following formula (XXIIa):
The compound may have the following formula (XXIII):
The compound may have the following formula (XXIIIa):
The compound may have the following Formula (XXIVa) or (XXIVb):
A method for synthesizing the compound of Formula (VI) as defined above may comprise the steps of providing a hydrazine and contacting the hydrazine with a functionalized cyclic group, wherein the cyclic group of the functionalized cyclic group is selected from the group comprising of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted tellurophene, optionally substituted pyrrole, optionally substituted phenylene, optionally substituted aza-phenylene, optionally substituted arylene diimide, optionally substituted fluorene, optionally substituted cabazole, optionally substituted dibenzodilole, optionally substituted benzooxodiazole, optionally substituted benzotriazole, optionally substituted benzothidiazole and any combination thereof.
The functionalized cyclic group may be functionalized with at least one nitrile (CN) group.
The functionalized cyclic group may be 2-cyanothiophene.
A method for synthesizing the compound of Formula (I) as defined above may comprise the steps of:
contacting the compound of Formula (IV) as defined above with the compound (VIIa) or (VIIb) as defined above under reaction conditions to form the compound of Formula (III) as defined above. The method for synthesizing the compound of Formula (I) as defined above may comprise an inverse-electron demanding Diels-Alder reaction. An inverse-electron demanding Diels-Alder reaction is an organic chemical reaction in which two new chemical bonds and a six-membered ring are formed. It is related to the Diels-Alder reaction, whereby an organic chemical reaction between a conjugated diene and a substituted alkene, commonly termed the dienophile, forms a substituted cyclohexene system. However, unlike the Diels-Alder reaction, the inverse electron demand Diels-Alder reaction is a cycloaddition between an electron-rich dienophile and an electon-poor diene. During an inverse-electron demand Diels-Alder reaction, three pi-bonds are broken and two sigma bonds and one new pi-bond are formed. In the present disclosure, the electronic nature of the reaction partners for an inverse Diels-Alder reaction is inversed again. The tetrazine, as the diene being used herein, may have electron-donating substituents, such as thiophenes, and is therefore considered electron-rich. The dienophile may be an intrinsically electron-poor moiety, such as an imide. This may result in synthetic challenges, which are solved by an inventive choice of solvents and reaction conditions.
The compounds of the formula (XXIVa) and (XXIVb) may both comprise electron withdrawing imides. The compounds of formula (XXIVa) and (XXIVb) may be reacted independently with the compound of Formula (I) to form the compound of Formula (III).
The compound of Formula (VIIa) or (VIIb) may be contacted with the compound of Formula (VI) to form P2 in the compound of Formula (I). When the compound of Formula (VIIa) is contacted with the compound of Formula (VI), P2 of the compound of Formula (I) may have the Formula (IIIa). When the compound of Formula (VIIb) is contacted with the compound of Formula (VI), P2 of the compound of Formula (I) may have the Formula (IIIb).
The method as defined above may be performed under reaction conditions. Reaction conditions may refer to the solvent, reaction temperature and duration of reaction. The choice of solvent, temperature and duration for the reaction for forming the compound of Formula (I) may be very important.
The solvent may be selected from the group consisting of chloroform, dichloromethane, tetrachloromethane, tetrahydrofuran, dioxane, diphenyl ether, toluene, chlorobenzene, dichlorobenzene, xylene and any mixture thereof. The solvent may not contain any reactivity towards the reaction mixture.
The reaction temperature may be in the range of about 40° C. to about 200° C., about 40 ° C. to about 60° C., about 40° C. to about 80° C., about 40° C. to about 100° C., about 40° C. to about 120° C., about 40° C. to about 140° C., about 40° C. to about 160° C., about 40° C. to about 180° C., about 60° C. to about 80° C., about 60° C. to about 100° C., about 60° C. to about 120° C., about 60° C. to about 140° C., about 60° C. to about 160° C., about 60° C. to about 180° C., about 60° C. to about 200° C., about 80° C. to about 100° C., about 80° C. to about 120° C., about 80° C. to about 140° C., about 80° C. to about 160° C., about 80° C. to about 180° C., about 80° C. to about 200° C., about 100° C. to about 120° C., about 100° C. to about 140° C., about 100° C. to about 160° C., about 100° C. to about 180° C., about 100° C. to about 200° C., about 120° C. to about 140° C., about 120° C. to about 160° C., about 120° C. to about 180° C., about 120° C. to about 200° C., about 140° C. to about 160° C., about 140° C. to about 180° C., about 140° C. to about 200° C., about 160° C. to about 180° C., about 160° C. to about 200° C. or about 180° C. to about 200° C. The boiling point of the solvent may be sufficiently high to allow the reaction to proceed.
The duration of reaction may be in the range of about 4 hours to about 24 hours, about 4 hours to about 6 hours, about 4 hours to about 8 hours, about 4 hours to about 10 hours, about 4 hours to about 12 hours, about 4 hours to about 18 hours, about 4 hours to about 24 hours, about 6 hours to about 8hours, about 6 hours to about 10 hours, about 6 hours to about 12 hours, about 6 hours to about 18hours, about 6 hours to about 24 hours, about 8 hours to about 10 hours, about 8 hours to about 12hours, about 8 hours to about 18 hours, about 8 hours to about 24 hours, about 10 hours to about 12hours, about 10 hours to about 18 hours, about 10 hours to about 24 hours, about 12 hours to about 18hours, about 12 hours to about 24 hours or about 18 hours to about 24 hours.
The reaction may proceed efficiently when diphenyl ether is used as the solvent and the reaction temperature is about 160° C. and the reaction duration is about 12 hours. If a solvent with a lower boiling point is used, for example, such that the reaction temperature cannot reach a sufficiently high temperature, the reaction may not proceed efficiently or at all even after 12 hours.
The method may further comprise the step of reacting the compound of Formula (III) as defined above with N-bromosuccinimide. The method may further comprise the step of reacting the compound of Formula (I) as defined above with N-bromosuccinimide and a peroxide, followed by a base when P2 of Formula (I) has the Formula (IIIc). When the P2 of the compound of Formula (I) has the Formula (IIIc), and this is reacted with N-bromosuccinimide and a peroxide, followed by a base, the resulting compound is the compound of Formula (I) where P2 has the Formula (IIId). The method may further comprise the step of reacting the compound of Formula (XVa) as defined above with N-bromosuccinimide and a peroxide, followed by a base, resulting in the formation of the compound of Formula (XVb).
The step of reacting the compound of Formula (I) as defined above with N-bromosuccinimide may be performed in a solvent selected from the group consisting of chloroform, trichloromethane, benzene and any mixture thereof.
The peroxide may be hydrogen peroxide or benzoyl peroxide. The peroxide may be benzoyl peroxide. The base may be triethylamine.
A method for synthesizing the compound of Formula (IV) as defined above may comprise the steps of:
A method for synthesizing the compound of Formula (IV) as defined above, comprising the steps of:
where Z may be a functional group containing zinc, tin or boron. Z may be Sn(CH3)3 or Sn(C4H9)3;
When q is 0, A8 may be S; X8 may be absent; A10, A11, A12 and A13 may be C, Z may be Sn(CH3)3 X10 may be H and X11 and X12 may be taken together to form an optionally substituted 7-membered heterocycloalkyl. The optionally substituted 7-membered heterocycloalkyl may be substituted with two alkoxy groups. The alkoxy groups may be OC12H25.
The compound of Formula (XXVI) may have the following formula (XXVIa):
The metal in the metal-containing catalyst may be selected from the group consisting of palladium, nickel and copper. The metal-containing catalyst may be Pd(PPh3)4.
The cross-coupling reagent may comprise tin. The cross-coupling reagent may comprise boron.
The cross-coupling reagent comprising tin may have the following formula (XXVII):
wherein R15 may be an optionally substituted alkyl.
The cross-coupling reagent comprising boron may have the following formula (XXVIIIa);
wherein R16 may be H or optionally substituted alkyl.
The cross-coupling reagent comprising boron may have the following formula (XXVIb) or (XXVIc):
P3/4 may refer to P3 or P4.
The cross-coupling reagent may have the following Formula (XXIXa), (XXIXb) or (XXIXc):
The cross-coupling reagent may have the following Formula (XXX):
Use of the compound as defined above may be in the manufacture of semiconductor devices. A semiconductor device may comprise the compound of Formula (IV) as defined above.
Non-limiting examples of the disclosure and a comparative example will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention.
The synthetic steps are disclosed in a general manner in the following synthetic methods. Variations of these general methods in order to produce the polymers according to the present disclosure are within the ability of the person skilled in the art. Where representative procedures are given, these can be adjusted by the person skilled in the art to other derivatives, if needed.
Pyridazines
Pyridazines synthesized having the following structure are shown in Table 1:
Phthalazines
Phthalazines synthesized having the following structure are shown in Table 2:
Some polymers synthesized from selected monomers in Tables 1 and 2 are shown in Table 3.
For all of polymers 1 to 12, b is an integer from 1 to 50.
The synthesis of a tetrazine precursor 1 is illustrated below:
3,6-Di(thiophen-2-yl)-1,2,4,5-tetrazine:
To a dried round bottom flask (1 L) was added 2-cyanothiophene (50 grams, 0.4587 mol), hydrazine (30% concentration, 50 mL), sulphur powder (1.47 grams, 0.04587 mol) and ethanol (200 mL). The mixture was stirred at 70° C. for 3 hours before cooling down to room temperature. Brown crystals were formed at the bottom of the solution. The crystals were collected by suction filtration and washed with cold ethanol (100 mL). After complete drying, the collected crystal was loaded into a dry round bottom flask (1 L). Isoamyl nitrite (107 grams, 0.9174 mol) and chloroform (200 mL) were added into the round bottom flask. The mixture was stirred at room temperature for 6 hours. The solvent was removed by rotary evaporation and the remaining solid was recrystallized in toluene to afford the target compound as a pure red crystal. Yield=47 grams, 84%.
General Synthesis of the Diels-Alder Product
The general synthetic scheme for the monomer synthesis is provided in
Diels-Alder Reaction—General Procedure for the Synthesis of the Compounds 3 and 5
To a dry round bottom flask was added the functionalized tetrazine compound (10 mmol), the dienophile moiety (10 mmol) and appropriate solvent. The solvent may be CHCl3, DCM, THF, dioxane, toluene, chlorobenzene, dichlorobenzene, xylene, etc. The mixture was heated to reflux overnight. After it was cooled down, the mixture was poured into cold methanol and the precipitate was collected via suction filtration. It was then thoroughly washed with cold methanol and used directly for the next step without further purification.
Elimination Step—General Procedure for the Synthesis of the Compound 6
To a dry round bottom flask was added the substrate (8 mmol), NBS (16 mmol) and appropriate solvent (chloroform, tetrachloromethane, benzene etc.), benzoyl peroxide (1 mmol). The mixture was heated to reflux overnight. After cooling down to room temperature, the mixture was poured into methanol. The precipitate was collected and used directly for the next step without further purification to yield the brominated product.
To a dry round bottom flask was added the brominated product (4 mmol), THF (10 ml) and triethylamine (10 ml). The mixture was stirred at room temperature overnight. The organic solvent was then removed and the target molecule was obtained by silica gel column chromatography.
The Stille Cross-Coupling Reaction for Polymer 1, Polymer 2 and Polymer 3
1,4-bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (24 mg, 0.032 mmol), 6,8-dibromo-3,3-bis((dodecyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine (200 mg, 0.281 mmol), and 2,5-bis(trimethylstannyI)thiophene(128 mg, 0.312 mmol) were dissolved in 12 ml of toluene, The mixture was stirred and purged with Argon for about 15 min, and then Pd(PPh3)4 (18.1 mg, 0.016 mmol) was added. The flask was purged with Argon for another 15 min before the mixture was heated to 110° C. for 48 hrs. Excess solvent was removed under reduced pressure and the polymer was precipitated with methanol. The suspension was filtered to give the crude product, which was then purified by Soxhlet extraction with acetone and chloroform. The chloroform fraction was evaporated to dryness to afford a purple-red solid.
The following stoichiometric ratio relative to 2,5-bis(trimethylstannyI)thiophene was used in the polymers:
1H NMR Characterization
Polymer 1. Yield 68%. 1H NMR (main signals) (CDCl3): δ 7.16-7.07 (br, s), 4.22 (br, s), 3.63-3.43 (br, m), 1.25 (br, s), 0.87 (br, s).
Polymer 2. Yield 70%. 1H NMR (main signals) (CDCl3); δ 7.06-7.00 (br, s), 4.16 (br, s), 3.62-3.42 (br, m), 1.25 (br, s), 0.88 (br, s).
Polymer 3. Yield 50%. 1H NMR (main signals) (CDCl3): δ 7.17-7.07 (br, s), 4.22 (br, s), 3.62-3.45 (br, m), 1.25 (br, s), 0.88 (br, s).
The GPC curves of these three polymers are shown in
UV-Vis Absorbance
The UV absorptions of solutions of the polymer 1, polymer 2 and polymer 3 in chlorobenzene in the wavelength range of 300 to 900 nm were recorded and are shown in
Indium tin oxide (ITO)/glass (15Ω/sq, 35×30×1.1mm) were used as substrates. The substrates were cleaned by successive sonication in acetone, isopropyl alcohol and DI water for 15 minutes each. They were then blown dry using nitrogen gas. Polymer solutions of polymers 1-3 were prepared at a concentration of 10 mg/ml using a mixed solvent system chloroform and chlorobenzene in a 6:4 volume ratio. The solutions were filtered through a 0.45 μm PVDF syringe filter prior to use. 80 μL of the polymer solution was pipetted onto the ITO/glass substrates and a polymer film was formed from spin-coating at 500 rpm for 60 seconds. The excessive polymer edges were removed by swabbing with chloroform using a cotton bud to obtain an active area of 2×2 cm2. On a second piece of cleaned ITO/glass substrate, an area of 2×2 cm2 was blocked out using parafilm. The total thickness of the parafilm spacer was kept constant at 0.01″. 250 μL of the gel electrolyte (0.512 g of lithium perchlorate and 2.8 g of poly(methyl methacrylate) (MW=120,000 g/mol) in 6.65 ml of propylene carbonate and 28 ml of dry acetonitrile) was pipetted within the 2×2 cm2 area and left to dry for 5 minutes.
The device was fabricated by assembling the two ITO/glass substrates together with the polymer film and gel electrolyte in contact. The device was secured using parafilm. A schematic depiction of the device thus produced is shown in
UV-Vis Absorbance
The UV-vis-NIR absorption spectra of the polymer devices at various applied potentials (V) for the polymer 1, polymer 2 and polymer 3 are recorded and shown in
Square-wave Potential Step Absorbance
The square-wave potential step absorptiometry of the polymer devices between 1.5 V and −1.5 V with a switch time of 10 seconds were recorded for the polymer 1, polymer 2 and polymer 3 and shown in
Optical and Electrochemical Properties
The optical and electrochemical properties of the polymers are shown in Table 5:
The performance of the electrochromic devices in visible light is shown in Table 6.
The performance of the electrochromic devices in Near Infra Red (NIR) is shown in Table 7.
Bleaching refers to the process in which the percent transmittance changes from a lower value to a higher value.
General Synthetic Scheme
The general synthetic scheme is provided in
Diels-Alder Reaction (Synthesis of Compound 9)
1,4-Bis(5-bromothiophen-2-yl)-7-(2-octyldodecyl)-5,5a,8a,9-tetrahydro-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (9).
To a dry round bottom flask was added 3,6-bis(5-bromothiophen-2-yl)-1,2,4,5-tetrazine (7) (3 g, 7.43 mmol), 2-(2-octyldodecyl)-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione (8) (3.19 g, 7.43 mmol) and diphenyl ether (a) (20 ml). The mixture was purged with argon for 15 min and then heated to 160° C. for 16 h. After cooling to room temperature, the mixture was directly subjected to silica gel column chromatography. Hexane was first used to flush away the diphenyl ether. The target compound was then collected as yellow oil using mixture solvent (Hex:CHCl3=1:1) then CHCl3 as eluent (5.10 g, 82%). The product was contaminated by ca. 5% of starting material. The crude product was used for the next step without further purification. HR-APCI-MS: m/z=804.1870, calculated exact mass: 804.1862, error: 0.9 ppm.
Elimination Reaction (Synthesis of Compound 10)
1,4-Bis(5-bromothiophen-2-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (10).
To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-7-(2-octyldodecyl)-5,5a,8a,9-tetrahydro-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (9) (1 g, 1.25 mmol), NBS (b) (2.2 equiv. 490 mg, 2.75 mmol), benzoyl peroxide (0.1 equiv, 0.125 mmol, 30 mg) and dichloroethane (c) (20 ml). The mixture was purged with argon for 15 min and then heated to 120° C. for 2 days. After cooling to room temperature, the solvent was removed by rotary evaporation. The residue was directly subjected to silica gel column chromatography to afford the target molecule as a yellow powder (720 mg, 72%). 1H NMR (400 MHz, CDCl3): δ ppm=8.93 (s, 2H), 7.52-7.51 (d, 2H, J=4 Hz), 7.28-7.27 (d, 2H, J=4 Hz), 3.71-3.69 (d, 2H, J=7.2 Hz), 1.94 (m, 1H), 1.29-1.23 (m, 32H), 0.88-0.84 (m, 6H). 13C NMR (100 MHz, CDCl3): δ ppm=166.84, 152.67, 140.05, 134.21, 131.63, 131.41, 127.56, 122.31, 119.06, 43.60, 37.41, 32.28, 31.89, 30.33, 30.02, 29.69, 26.66, 23.06, 14.50. HR-EI-MS: m/z=801.1470, calculated exact mass: 801.1456, error: 1.81 ppm.
The 1H NMR, 13C NMR and HRMS spectra of this compound (compound 10) are provided in
Cross-Coupling Reaction (Synthesis of Compound 12)
1,4-Bis(5-(3,3-bis((dodecyloxy)methy)-3,4-dihydro-2H-theino[3,4-b][1,4]dioxepin-6-yl)thiophene-2-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (12).
To a dry round bottom flask was added (3,3-bis((dodecyloxy)methyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)trimethylstannane (11) (2 g, 50% purity), 1,4-bis(5-bromothophen-2-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (10) (370 mg, 0.47 mmol), Pd(PPh3)4 (0.1 equiv, 0.047 mmol, 54 mg) and dry toluene (15 ml). The mixture was degassed by purging with argon and then heated to 110° C. for 16 h. After cooling to room temperature, the solvent was removed by rotary evaporation. The collected residue was dissolved in minimum amount of chloroform and directly subjected to silica gel column chromatography. The target compound was then collected as red waxy solid using a solvent mixture (Hex:CHCl3=1:1) (510 mg, 62%). The target compound was found to be unstable at ambient condition. It was stored in the fridge after preparation. 1H NMR (400 MHz, CDCl3): δ ppm=9.00 (s, 2H), 7.68 (d, 2H, J=3.6 Hz),7.38-7.37 (d, 2H, J=4 Hz), 6.45 (s, 2H), 4.22 (s, 4H), 4.10 (s, 4H), 3.71-3.69 (d, 2H, J=7.2 Hz), 3.55 (m, 8H), 3.44-3.41 (m, 8H), 1.94 (m, 1H), 1.68 (m, 4H), 1.56-1.54 (m, 8H), 1.30-1.24 (m, 100H), 0.88-0.85 (m, 18H). 13C NMR (100 MHz, CDCl3): δ ppm=167.06, 152.76, 150.41, 147.06, 141.15, 136.18, 134.00, 131.31, 127.99, 123.98, 122.81, 116.59, 103.85, 74.41, 72.20, 70.00, 48.25, 43.53, 37.41, 32.33, 31.89, 30.36, 30.08, 29.97, 29.77, 26.58, 23.09, 14.52. HR-APCI-MS: m/z=1744.1423, calculated exact mass: 1744.1411, error: 0.67 ppm.
Bromination Reaction (Synthesis of Compound 13)
1,4-Bis(5-(8-bromo-3,3-bis((dodecyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]-phthalazine-6,8(7H)-dione (13).
To a dry round bottom flask was added 1,4-Bis(5-(3,3-bis((dodecyloxy)methy)-3,4-dihydro-2H-theino[3,4-b][1,4]dioxepin-6-yl)thiophene-2-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (12) (1 g, 0.573 mmol), NBS (b) (2.2 equiv., 1.26 mmol, 225 mg) and chloroform (10 ml). The mixture was stirred at room temperature overnight. The solvent was removed by rotary evaporation and the residue was directly subjected to silica gel chromatography using hexane: chloroform (1:1) to afford the target product as a red waxy solid (0.92 g, 85%). NMR (400 MHz, CDCl3): δ ppm=8.98 (s, 2H), 7.66-7.65 (d, J=4 Hz, 2H), 7.30-7.29 (d, J=4 Hz, 2H), 4.22 (s, 4H), 4.17 (s, 4H), 3.71-3.69 (d, J=7.2 Hz, 2H), 3.55 (s, 8H), 3.44-3.41 (t, J=6.4 Hz, 8H), 1.91 (m, 1H), 1.55-1.24 (m, 112H), 0.88-0.85 (m, 18H). 13C NMR (100 MHz, CDCl3): δ ppm=167.02, 152.76, 148.45, 145.93, 139.98, 133.99, 131.14, 127.78, 124.09, 123.11, 122.72, 116.27, 92.92, 74.67, 72.19, 69.90, 48.31, 43.53, 37.43, 32.31, 31.89, 30.35, 30.09, 26.60, 23.11, 14.54. HR-APCI-MS: m/z=1901.9589, calculated exact mass: 1901.9568, error: 1.17 ppm.
Stille Cross-coupling Polymerization.
1,4-Bis(5-(8-bromo-3,3-bis((dodecyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4] dioxepin-6-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]-phthalazine-6,8(7H)-dione (13) (300 mg, 0.158 mmol) and bis(trimethylstannyl) compounds 14 (0.158 mmol) were dissolved in 10 ml of toluene. The mixture was stirred and purged with argon for about 15 min, and then Pd(PPh3)4 (6% equiv., 0.00948 mmol, 11 mg) was added. The flask was purged with argon for another 15 min before the mixture was heated to 110° C. for 2 days. Excess solvent was removed under reduced pressure and the polymer was precipitated with methanol. The suspension was filtered to give the crude product, which was then purified by Soxhlet extraction with acetone and chloroform. The chloroform fraction was evaporated to dryness to afford the target polymer materials 15.
The bis(trimethylstannyl) compounds 14 were as follows:
1H NMR Characterization
Polymer 4. Yield 74%. 1H NMR (main signals) (CDCl3): δ 9.09 (br), 7.92 (br), 4.31 (br, m), 3.72-3.45 (br, m), 1.68-1.58 (br, m), 1.24 (m), 0.87 (m).
Polymer 5. Yield 72%. NMR (main signals) (CDCl3): δ 8.99 (br), 7.65 (br), 4.33 (br), 3.62-3.48 (br, m), 1.24 (br, m), 0.86 (br, m).
Polymer 6. Yield 55%. 1H NMR (main signals) (CDCl3): δ 9.08 (br), 7.82 (br), 6.97 (br), 4.31 (br), 3.70-3.48 (br, m), 1.79-1.68 (br), 1.24 (br), 0.86 (br).
The NMR spectra of these Polymer 4, Polymer 5 and Polymer 6 are provided in
Prior to use, ITO/glass substrates were cleaned by successive ultrasonication in acetone, isopropyl alcohol and distilled water, and blown dry with N2. Polymer solutions of polymer 4, polymer 5 and polymer 6 were prepared at a concentration of 15 mg/mL in 6:4 (v/v) chloroform:chlorobenzene mixed solvent. Warm polymer solution (50° C.) was filtered and spin-coated onto the heated ITO substrates (50° C.) at 1200 rpm for 60 seconds to yield film thickness of around 100 nm. For drop-cast films, the polymer solutions are dispensed, spread onto the ITO substrates and left to dry. Film thickness of approximately 150-200 nm was obtained. Excessive polymer edges were removed by swabbing with chloroform using a cotton bud to obtain an active area of 2×2 cm2. On a second piece of ITO substrate, an area of 2×2 cm2 was blocked out using parafilm. The total thickness of the parafilm spacer and barrier was kept constant at 0.01″. 250 μL of the gel electrolyte (0.512 g of lithium perchlorate and 2.8 g of poly(methyl methacrylate) (MW=120,000 g/mol) in 6.65 ml of propylene carbonate and 28 ml of dry acetonitrile) was pipetted within the 2×2 cm2 area. The device was fabricated by assembling the two ITO/glass substrates together with the polymer film and gel electrolyte in contact.
Electron Capture (EC) Electrospectroscopy
The electron capture (EC) electrospectroscopy of the polymer 5 in a EC device is depicted in
The electrochromic performance of the polymer devices of Polymer 4, Polymer 5 and Polymer 6 are summarized in the following Table 8:
The optical contrast refers to how much the color of the film has changed upon an applied voltage. Polymers 4, 5 and 6 showed reasonably good optical contrast in the visible region and good contrast in the NIR region. The bleaching time and coloration time refer to how fast the device changes its color. Polymers 4, 5 and 6 showed good coloration time below 5 seconds. This means that upon an applied voltage, the thin film device will reach their full optical contrast in less than 5 seconds. The coloration efficiency describes how much electricity is needed to power the polymer device. The coloration efficiency for this batch of polymers is generally good with values greater than 200 cm2/C.
Time-dependent density-functional theory calculation is carried out to compare the magnitude of electron deficiency of the imide-fused pyridazines with current commonly used electron deficient acceptors. The results shown in
Monomer 1:
1,4-Bis(5-bromothiophen-2-yl)-6-hexyl-5H-pyrrolo[3,4-d]-pyridazine-5,7(6H)-dione
To a dry round bottom flask was added 3,6-bis(5-bromothiophen-2-yl)-1,2,4,5-tetrazine (300 mg, 0.743 mmol), 1-(2-hexyl)-1H-pyrrole-2,5-dione (135 mg, 0.743 mmol) and diphenyl ether (10 ml). The mixture was purged with argon for 15 min and then heated to 160° C. for 16 h. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Hexane was used first to flush away the diphenyl ether. The target compound was then collected as yellow powder using mixture solvent (Hex:CHCl3=1:1) then CHCl3 as eluent (230 mg, 56%). 1H NMR (400 MHz, CDCl3): δ ppm=8.62-8.61 (d, J=4 Hz, 2H), 7.20-7.18 (d, J=3.6 Hz, 2H), 3.79-3.76 (t, J=7.6 Hz, 2H), 1.72-1.67 (m, 2H), 1.33 (m, 6H), 0.91-0.87 (t, J=6.4 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ ppm=167.47, 148.32, 139.74, 134.33, 132.09, 122.57, 121.47, 39.64, 31.66, 28.58, 26.92, 22.87, 14.40. HR-EI-MS: m/z=552.9136, calculated exact mass: 552.9123, error: 2.28 ppm.
Monomer 3:
1,4-Bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione:
To a dry round bottom flask was added 3,6-bis(5-bromothiophen-2-yl)-1,2,4,5-tetrazine (3 g, 7.43 mmol), 1-(2-octyldodecyl)-1H-pyrrole-2,5-dione (2.8 g, 7.43 mmol) and diphenyl ether (20 ml). The mixture was purged with argon for 15 min and then heated to 160° C. for 16 h. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Hexane was used first to flush away the diphenyl ether. The target compound was then collected as yellow powder using mixture solvent (Hex:CHCl3=1:1) then CHCl3 as eluent (3.42 g, 62%). 1H NMR (400 MHz, CDCl3): δ ppm=8.63-8.62 (d, J=4 Hz, 2H), 7.19-7.18 (d, J=4 Hz, 2H), 3.67-3.65 (d, J=7.2 Hz, 2H), 1.90 (m, 1H), 1.25-1.24 (m, 32H), 0.89-0.85 (m, 6H). 13C NMR (100 MHz, CDCl3): δ ppm=167.72, 148.30, 139.78, 134.38, 132.09, 122.47, 121.47, 43.81, 37.37, 32.31, 32.27, 31.85, 30.31, 30.02, 29.97, 29.93, 29.75, 29.68, 26.62, 23.08, 14.52. HR-EI-MS: m/z=750.1408, calculated exact mass: 750.1393, error: −2.1 ppm.
Monomer 4:
1,4-Bis(5-bromofuran-2-yl)-6-hexyl-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione:
To a dry round bottom flask was added 3,6-bis(5-bromofuran-2-yl)-1,2,4,5-tetrazine (300 mg, 0.81 mmol), 1-(2-hexyl)-1H-pyrrole-2,5-dione (146 mg, 0.81 mmol) and diphenyl ether (10 ml). The mixture was purged with argon for 15 min and then heated to 160° C. for 16 h. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Hexane was used first to flush away the diphenyl ether. The target compound was then collected as yellow powder using mixture solvent (Hex:CHCl3=1:1) then CHCl3 as eluent (310 mg, 73%). 1H NMR (400 MHz, CDCl3): δ ppm=8.03-8.02 (d, J=3.6 Hz, 2H), 6.62-6.61 (d, J=4 Hz, 2H), 3.77-3.73 (t, J=7.6 Hz, 2H), 1.70-1.65 (m, 2H), 1.32 (m, 6H), 0.89-0.86 (t, J=6.4 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ ppm=167.72, 148.30, 139.78, 134.38, 132.09, 122.47, 121.47, 43.81, 37.37, 32.31, 32.27, 31.85, 30.31, 30.02, 29.97, 29.93, 29.75, 29.68, 26.62, 23.08, 14.52. HR-EI-MS: m/z=520.9586, calculated exact mass: 520.9580, error: 1.04 ppm.
Monomer 6:
1,4-Bis(5-bromofuran-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione:
To a dry round bottom flask was added 3,6-bis(5-bromofuran-2-yl)-1,2,4,5-tetrazine (1.48 g, 4 mmol), 1-(2-octyldodecyl)-1H-pyrrole-2,5-dione (4 mmol, 1.51 g) and diphenyl ether (15 ml). The mixture was degassed by purging with argon and then heated to 160° C. for 16 h. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Hexane was used first to flush away the diphenyl ether. The target compound was then collected as yellow powder using mixture solvent (Hex:CHCl3=1:1) then CHCl3 as eluent (1.86 g, 65%). 1H NMR (400 MHz, CDCl3): δ ppm=8.06 (d, 2H, J=3.6 Hz), 6.64-6.63 (d, 2H, J=3.6 Hz), 3.66-3.64 (d, 2H, J=7.6 Hz), 1.57 (m, 1H), 1.24 (m, 32H), 0.89-0.85 (m, 6H). 13C NMR (100 MHz, CDCl3): δ ppm=166.89, 149.69, 143.31, 128.45, 122.25, 121.37, 115.17, 43.77, 37.29, 32.30, 31.81, 30.30, 30.01, 29.73, 29.67, 26.59, 23.07, 14.51. HR-EI-MS: m/z=719.1476, calculated exact mass: 719.1756, error: −1.41 ppm.
Monomer 10—Step 1:
1,4-Bis(5-bromothiophen-2-yl)-7butyl-5,5a,8a,9-tetrahydro-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione:
To a dry round bottom flask was added 3,6-bis(5-bromothiophen-2-yl)-1,2,4,5-tetrazine (400 mg, 0.1 mmol), 2-butyl-3a,4,7,7a-tetrahydro-1H-isoindole 1,3(2H)-dione (207 mg, 0.1 mmol) and diphenyl ether (10 ml). The mixture was purged with argon for 15 min and then heated to 160° C. for 16h. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Hexane was used first to flush away the diphenyl ether. The target compound was then collected as yellow powder using mixture solvent (Hex:CHCl3=1:1) then CHCl3 as eluent (410 mg, 71%). 1H NMR (400 MHz, CDCl3): δ ppm=7.32-7.31 (d, J=4 Hz, 2H), 7.16-7.15 (d, J=4 Hz, 2H), 3.83-3.79 (m, 2H), 3.44-3.42 (m, 2H), 3.38-3.35 (t, J=6.8 Hz, 2H), 2.94-2.90 (m, 2H), 1.27-1.22 (m, 2H), 0.74-0.70 (t, J=6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ ppm=178.33, 151.97, 140.45, 133.24, 131.26, 129.88, 117.50, 39.39, 38.88, 29.69, 25.21, 19.85, 13.80. HR-EI-MS: m/z=580.9288, calculated exact mass: 580.9265, error: 3.94 ppm.
The HR-EI MS spectrum for this intermediate is shown further below as
Monomer 10—Step 2:
1,4-Bis(5-bromothiophen-2-yl)-7-butyl-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione:
To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-7-butyl-5,5a,8a,9-tetrahydro-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (200 mg, 0.345 mmol), NBS (2.2 equiv., 0.76 mmol, 135 mg), BPO (0.1 equiv. 0.0345 mol, 10 mg) and dichloroethane (10ml). The mixture was purged with argon for 10 min and then heated to 120° C. for 2 days. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Chloroform was used as the eluent and the target product was obtained as a yellow solid. (135 mg, 68%) 1H NMR (400 MHz, CDCl3): δ ppm=.8.92 (s, 2H), 7.52-7.51 (d, J=4 Hz, 2H), 7.29-7.28 (d, J=3.6 Hz, 2H), 3.83-3.80 (t, J=7.2 Hz, 2H), 1.76-1.68 (m, 2H), 1.45-1.37 (m. 2H), 0.99-0.95 (t, J=7.6 Hz, 3H) 13C NMR (100 MHz, CDCl3): δ ppm=166.52, 152.63, 139.69, 134.39, 131.69, 131.61, 127.66, 122.35, 119.26, 39.14, 30.82, 20.49, 14.00. HR-EI-MS: m/z=572.8961, calculated exact mass: 576.8952, error: 1.65 ppm.
Polymer 7:
To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (225 mg, 0.3 mmol), 2,2′-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(1,3,2-dioxaborinane) (168 mg, 0.3 mmol), Pd(PPh3)4 (6 mol %, 0.018 mmol, 21 mg), K2CO3 (2 mmol, 276 mg), H2O (1 ml), toluene (10 ml) and Aliquat 336 (catalytic amount). The mixture was purged with argon for 30 min and then heated to 100° C. for 48 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The red precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (250 mg, 85%)
Polymer 8:
To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (225 mg, 0.3 mmol), 9-(2-dodecyl)-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (210 mg, 0.3 mmol), Pd(PPh3)4 (6 mol %, 0.018 mmol, 21 mg), K2CO3 (2 mmol, 276 mg), H2O (1 ml), toluene (10 ml) and Aliquat 336 (catalytic amount). The mixture was purged with argon for 30 min and then heated to 100° C. for 48 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The purple precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (250 mg, 85%)
Polymer 9:
To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (225 mg, 0.3 mmol), (4,8-bis(octyloxy)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl)bis(trimethylstannane) (232 mg, 0.3 mmol), Pd2(dba)3 (3 mol %, 0.009 mmol, 8.5 mg), P(o-tol)3 (12 mol %, 0.036 mmol, 11 mg) and toluene (10 ml). The mixture was purged with argon for 30 min and then heated to 100° C. for 16 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (230 mg, 74%)
Polymer 10:
To a dry round bottom flask was added 1,4-bis(5-bromofuran-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (216 mg, 0.3 mmol), (4,8-bis(octyloxy)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl)bis(trimethylstannane) (232 mg, 0.3 mmol), Pd2(dba)3 (3 mol %, 0.009 mmol, 8.5 mg), P(o-tol)3 (12 mol %, 0.036 mmol, 11 mg) and toluene (10 ml). The mixture was purged with argon for 30 min and then heated to 100° C. for 16 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (215 mg, 72%)
Polymer 11:
To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (225 mg, 0.3 mmol), (4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl)bis(trimethylstannane) (232 mg, 0.3 mmol), Pd2(dba)3 (3 mol %, 0.009 mmol, 8.5 mg), P(o-tol)3 (12 mol %, 0.036 mmol, 11 mg) and toluene (10 ml). The mixture was purged with argon for 30 min and then heated to 100° C. for 16 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (210 mg, 68%)
Polymer 12:
To a dry round bottom flask was added 1,4-bis(5-bromofuran-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (216 mg, 0.3 mmol), (4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl)bis(trimethylstannane) (232 mg, 0.3 mmol), Pd2(dba)3 (3 mol %, 0.009 mmol, 8.5 mg), P(o-tol)3 (12 mol %, 0.036 mmol, 11 mg) and toluene (10 ml). The mixture was purged with argon for 30 min and then heated to 100° C. for 16 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (200 mg, 67%)
The compounds of Formula (VI), (VIIa) and (VIIb) as defined above may be useful in the manufacture of the compounds of Formula (I). The compound of Formula (I) may be useful in the manufacture of the compounds of Formula (IV). The compounds of Formula (IV) may be useful in the manufacture of semiconductor devices. The semiconductor devices manufactured using the compound of Formula (IV) as defined above may be used in a wide range of applications such as electrochromic materials, organic light-emitting diode, organic thin-film transistors and organic photovoltaic cells. As the NIR absorption properties can be reversibly switched by applying/removing a low voltage on the thin film, the materials may have applications in smart glass or smart window applications.
It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10201404150Q | Jul 2014 | SG | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/SG2015/050218 | 7/16/2015 | WO | 00 |
