Patent Application
20230413661
Described herein are a novel class of gold(III) compounds that display a novel concept of thermally stimulated delayed phosphorescence (TSDP) as well as the development of a new class of TSDP emitters as exemplified by the novel class of gold(III) compounds with TSDP properties and the syntheses of these compounds. Also disclosed herein are compounds that can be used as light-emitting materials for phosphorescent organic light-emitting devices (PHOLEDs) and methods of making and using the compounds themselves.
Taking the advantages of low cost, light weight, low power consumption, high brightness, excellent color tunability, wide viewing angle of up to 180 degrees as well as their ease of fabrication onto flexible substrates, organic light-emitting devices (OLEDs) are considered to be remarkably attractive candidates for flat panel display technologies and solid-state lighting systems. Typically, an OLED consists of several layers of semiconductors sandwiched between two electrodes. The cathode is composed of a low work function metal or metal alloy deposited by vacuum evaporation, whereas the anode is a transparent conductor such as indium tin oxide (ITO). Upon application of a direct current (DC) voltage, holes injected from the ITO anode and electrons injected from the metal cathode will recombine to form excitons. Subsequent relaxation of excitons then results in the generation of electroluminescence (EL).
The breakthroughs that led to the exponential growth of this field and to its first commercialized products can be traced to two pioneering demonstrations. In 1987, Tang and VanSlyke [Tang, C. W; VanSlyke, S. A. Appl. Phys. Lett. 51, 913 (1987)] proposed the use of a double-layer structure of vacuum deposited, small-molecular films, in which tris(8-hydroxyquinoline)aluminum (Alq3) was utilized both as light-emitting layer and electron-transporting layer. Later, the first polymeric light-emitting device was pioneered by Burroughs et al. in 1990 [Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R. N.; Mackay, K.; Friend, R. H.; Burns, P. L.; Holmes, A. B. Nature 347, 539 (1990)], in which a yellow-green EL from poly(p-phenylenenvinylene) (PPV) was achieved. Since then, a number of electroluminescent small molecule based and polymeric light-emitting materials have been investigated with improved light-emitting properties. The key advantage of using polymers as light-emitting materials is that they are highly soluble in most organic solvents, and OLEDs can be easily fabricated by using low-cost and efficient wet-processing techniques, such as spin-coating, screen-printing, or ink-jet printing [Burrows, P. E.; Forrest, S. R.; Thompson, M. E. Curr. Opin. Solid State Mater. Sci. 2, 236 (1997)].
In 1998, Forrest and Thompson demonstrated the use of a transition metal complex, 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine platinum(II) [Pt(OEP)] as emitter and fabricated highly efficient phosphorescent OLEDs with external quantum efficiency (EQE) of approximately 4% [Baldo, M. A.; O'Brien, D. F.; You, Y; Shoustikov, A.; Sibley, S.; Thompson, M. E.; Forrest, S. R. Nature 395, 151 (1998)]. The introduction of a heavy metal center into an organic framework can effectively lead to a strong spin-orbit coupling and thus promote an efficient intersystem crossing from the singlet excited state to the lower-energy triplet excited state to give phosphorescence. This can result in theoretically a four-fold enhancement in the internal quantum efficiency (IQE) of the OLEDs up to 100% upon the harvesting of both triplet and singlet excitons. This breakthrough has aroused enormous research interest on the development of high performance triplet emitters based on iridium(III) and platinum(II) systems, and highly efficient OLEDs with EQEs of up to 30% have been recently achieved.
In addition to the well-established iridium(III) and platinum(II) systems, cyclometalated gold(III) complexes are another class of promising phosphorescent emitters because of their high luminescence quantum yields, short excited-state lifetimes, and high thermal and electrochemical stabilities. In 2005, Yam and co-workers incorporated strong σ-donating alkynyl ligands into the gold(III) framework and generated a series of bis-cyclometalated alkynylgold(III) compounds. These gold(III) complexes exhibit rich luminescence behaviors at both room and low temperatures in various media [Wong, K. M.-C.; Zhu, X.; Hung, L.-L.; Zhu, N.; Yam, V. W.-W.; Kwok, H.-S. Chem. Commun. 2906 (2005); Yam, V. W.-W.; Wong, K. M.-C.; Hung, L.-L.; Zhu, N. Angew. Chem. Int. Ed. 44, 3107 (2005); Wong, K. M.-C.; Hung, L.-L.; Lam, W. H.; Zhu, N.; Yam, V. W.-W. J. Am. Chem. Soc. 129, 4350 (2007)]. Notably, the emission colors of these gold(III) complexes can be fine-tuned to span the entire visible spectrum by variation of different substituents on the cyclometalating pincer or alkynyl ligands. High performance OLEDs with current efficiency of 37.4 cd A−1 and EQEs of 11.5% have also been reported [Au, V. K.-M.; Wong, K. M.-C.; Tsang, D. P.-K.; Chan, M.-Y; Zhu, N.; Yam, V. W.-W. J. Am. Chem. Soc. 132, 14273 (2010)]. Recently, the same research group also developed new classes of solution-processable gold(III) complexes by incorporating the gold(III) emitter within a dendritic structure [Tang, M.-C.; Tsang, D. P.-K.; Chan, M. M.-Y; Wong, K. M.-C.; Yam, V. W.-W. Angew. Chem. Int. Ed. 52, 446 (2013); Tang, M.-C.; Chan, C. K.-M.; Tsang, D. P.-K.; Wong, Y.-C.; Chan, M. M.-Y; Wong, K. M.-C.; Yam, V. W.-W. Chem. Eur. J. 20, 15233 (2014); Lee, C.-H.; Tang, M.-C.; Wong, Y.-C.; Chan, M.-Y; Yam, V. W.-W. J. Am. Chem. Soc. 139, 10539 (2017)]. Meanwhile, bipolar gold(III) complexes having N-phenylbenzimidazole as an acceptor and triphenylamine as a donor have been developed [Tang, M.-C.; Tsang, D. P.-K.; Wong, Y.-C.; Chan, M.-Y; Wong, K. M.-C.; Yam, V. W.-W. J. Am. Chem. Soc. 136, 17861 (2014)]. Solution-processable OLEDs with high EQE of up to 10% and an extremely small efficiency roll-off value of less than 1% at the practical brightness level of 1000 cd m−2 have been demonstrated. The recent use of post-synthetic ligand modification approach has generated a new class of tetradentate gold(III) complexes with high thermal stability and extraordinarily high photoluminescence quantum yields (PLQYs) of up to 78% have been realized [Wong, B. Y.-W.; Wong, H.-L.; Wong, Y.-C.; Chan, M.-Y; Yam, V. W.-W. Angew. Chem. Int. Ed. 56, 302 (2017)].
Remarkable discoveries on metal-free organic materials with thermally activated delayed fluorescence (TADF) properties have injected a new twist to the field of OLEDs. In particular, a rational design on the molecular structure to generate a small energy gap between the lowest energy triplet (T1) state and the lowest energy singlet (S1) state can make possible the up-conversion from the triplet excitons to the singlet excitons by reverse intersystem-crossing (RISC). The newly generated singlet excitons then decay through radiative transition and give out delayed fluorescence (DF). With a high rate of RISC and small energy gaps between S1 and T1, a 100% exciton utilization can be achieved. The first report on TADF can be dated back to 1961, contributed by Parker and Hatchard in the eosin dye, and was subsequently named “E-type” delayed fluorescence. The second band of long-lived emission besides phosphorescence was found to be of identical profile as the prompt fluorescence band, and was assigned to be DF from the same excited singlet state [Parker, C. A.; Hatchard, C. G. Trans. Faraday Society 57, 1894 (1961)]. The first metal-containing TADF material was observed in a copper(I) complex by Blasse and co-workers in 1980, in which another emission mechanism with two excited states in thermal equilibrium was proposed [Blasse, G.; McMillin, D. R. Chem. Phys. Lett. 70, 1 (1980)]. In the late 1990s, the efficient delayed fluorescence was further verified in fullerenes by Berberan-Santos and co-workers, with the derivation of rate equations to describe the mechanism [Berberan-Santos, M. N.; Garcia, J. M. M. J. Am. Chem. Soc. 118, 9391 (1996)]. Despite the early success of the research on TADF, this type of material was not applied on OLEDs until 2009, pioneered by Adachi and co-workers, who realized TADF based OLEDs by utilizing a Sn(IV)-porphyrin complex [Endo, A.; Ogasawara, M.; Takahashi, A.; Yokoyama, D.; Kato, Y.; Adachi, C. Adv. Mater. 21, 4802 (2009)]. Continuing this concept, the same group reported the first purely organic TADF emitter in 2011, which showed a 5.3% EQE in OLEDs, approaching the theoretical practical limit for singlet emitters [Endo, A.; Sato, K.; Yoshimura, K.; Kai, T.; Kawada, A.; Miyazaki, H.; Adachi, C. Appl. Phys. Lett. 98, 083302 (2011)]. In 2012, a series of organic TADF emitters were reported by the same group, in which an EQE of 19.3% was achieved in the best performing devices, well-beyond the theoretical practical maximum of 5% for singlet emitters [Uoyama, H.; Goushi, K.; Shizu, K.; Nomura, H.; Adachi, C. Nature 492, 234 (2012)]. Since then, TADF emitters have been an important topic in both academic and industrial research. With the continuous effort of researchers in this field, EQEs of OLEDs have been reported reaching 36.7% for blue [Lin, T.-A.; Chatterjee, T.; Tsai, W.-L.; Lee, W.-K.; Wu, M.-J.; Jiao, M.; Pan, K.-C.; Yi, C.-L.; Chung, C.-L.; Wong, K.-T.; Wu, C.-C. Adv. Mater 28, 6976 (2016)], 29.6% for green [Kaji, H.; Suzuki, H.; Fukushima, T.; Shizu, K.; Suzuki, K.; Kubo, S.; Komino, T.; Oiwa, H.; Suzuki, F.; Wakamiya, A.; Murata, Y; Adachi, C. Nat. Commun. 6, 8476 (2015)] and 17.5% for red [Li, J.; Nakagawa, T.; MacDonald, J.; Zhang, Q.; Nomura, H.; Miyazaki, H.; Adachi, C. Adv. Mater 25, 3319 (2013)].
Apart from RISC from the lowest-energy T1 state to the S1 state to generate fluorescence, RISC can also occur from the higher triplet Tn excited states to the S1 state provided that the energy gap between the S1 and Tn excited states are sufficiently small. This allows the emitters to effectively harvest both singlet and triplet excitons, as reported by Ma and co-workers in 2014 [Li, W.; Pan, Y; Yao, L.; Liu, H.; Zhang, S.; Wang, C.; Shen, F.; Lu, P.; Yang, B.; Ma, Y Advanced Optical Materials 2, 892 (2014)].
Another approach to harvest all singlet and triplet excitons is the effective mixing of localized electron (LE) state and charge transfer (CT) state to form the hybridized local and charge transfer (HLCT) state [Li, W.; Pan, Y; Xiao, R.; Peng, Q.; Zhang, S.; Ma, D.; Li, F.; Shen, F.; Wang, Y; Yang, B.; Ma, Y Adv. Funct. Mater 24, 1609 (2014)]. The weak binding energy of the CT state allows the spin mixing between singlet and triplet states, in which a spin flip between singlet and triplet excitons becomes feasible, achieving singlet exciton harvesting with a singlet-to-triplet ratio of larger than 25%. Yet, the forbidden electronic transition from the total spatial separation of orbitals generally results in very low fluorescence efficiency. Meanwhile, the LE state is a highly efficient radiative state, arising from its large transition dipole moment with a larger orbital overlap. By mixing the above-mentioned states into the HLCT state, both singlet and triplet excitons can be harvested with high efficiency. Recently, OLEDs utilizing the HLCT state with decent EQEs have been reported; in particular, a maximum EQE of 2.8% for deep red[Li, W.; Pan, Y.; Yao, L.; Liu, H.; Zhang, S.; Wang, C.; Shen, F.; Lu, P.; Yang, B.; Ma, Y. Advanced Optical Materials 2, 892 (2014)], 6.9% for green [Wang, C.; Li, X.; Pan, Y.; Zhang, S.; Yao, L.; Bai, Q.; Li, W.; Lu, P.; Yang, B.; Su, S.; Ma, Y. ACS Appl. Mater. Interfaces 8, 3041 (2016)], and 6.8% for deep blue emission have been demonstrated, respectively [Tang, X.; Bai, Q.; Peng, Q.; Gao, Y.; Li, J.; Liu, Y.; Yao, L.; Lu, P.; Yang, B.; Ma, Y. Chem. Mater. 27, 7050 (2015)].
At the same time, the concept of thermally equilibrated excited (thexi) states has been introduced to discuss the thermal equilibrium between two excited states in 1976, similar to the TADF [Adamson, A. W. Inorganic Compounds with Unusual Properties 128 (1976)]. However, such excited states are in thermodynamic equilibrium with the surroundings and are the high-energy isomers of the ground state. The transfer of excitons between thexi states usually involves reaction of excited states, such as the ligand field substitutional photochemistry of trans- and cis-[Co(en)2(NH3)Cl]2+, but is not related to emissive states and luminescence.
However, the known methods described above have drawbacks. Even though superior EL efficiency has been achieved in blue-emitting OLEDs, their operational stability is much more inferior when compared to their red- and green-emitting OLED counterparts. The direct formation of high energy triplet excitons tends to facilitate the dissociation of chemical bonds, rendering the development of stable deep blue triplet emitters more challenging. Thus, the field has a need to develop emitters that emit in the desirable high-energy blue region, but possess the lowest-energy triplet state in the blue-green or green region to minimize photodegradation of the chemical bonds, i.e., the triplet emission comes from a higher-energy triplet (T1′) state rather than the lowest-energy triplet (T1) state.
It is in regard to these issues and others that the present disclosure is provided.
In one or more embodiments, compounds having properties of thermally stimulated delayed phosphorescence (TSDP) are provided. In one or more embodiments, the compounds capable of TSDP are formed as TSDP emitters. In one or more embodiments, a novel class of gold(III) compounds having a triazine-containing cyclometalating tridentate ligand that exhibits TSDP properties and their syntheses is provided. In one or more embodiments, OLEDs based on these novel luminescent gold(III) compounds with TSDP properties are provided.
The novel TSDP is realized by using efficient spin-allowed RIC to harvest emission from the higher-energy T1′ excited state via the up-conversion from the T1 state.
In one or more embodiments, the novel luminescent gold(III) compounds contain a triazine-containing cyclometalating tridentate ligand and one strong σ-donating group, both coordinated to a gold(III) metal center.
In one or more embodiments, novel luminescent gold(III) compounds with TSDP properties have the chemical structure shown in the generic formula (I) and (II) are provided,
in which:
In one or more embodiments, the compound is deposited as a thin layer on a substrate. For example, the thin layer can be deposited by vacuum deposition, spin-coating, or inkjet printing. In one or more embodiments, the luminescent gold(III) compounds disclosed herein are deposited as a thin layer on a substrate layer. In one or more embodiments, the thickness of the deposited gold(III) compound is 10-20 nm, 21-30 nm, 31-40 nm, 41-50 nm, 51-60 nm, 61-70 nm, 71-80 nm, 81-90 nm, or 91-100 nm. Further, the compound has photoluminescence properties within a range of about 380 to 1050 nm.
In one or more embodiments, the gold(III) compound is a dopant in the light-emitting layer or emissive layer of an OLED. For example, an emission energy of the OLED can be independent or dependent on the concentration of the gold(III) compound and one or more donor groups on an auxiliary ligand, in which the one or more donor groups are selected from, but not limited to: N, S, O, P.
In accordance one or more embodiments disclosed herein, the novel class of gold(III) compounds show either strong photoluminescence (PL) via a triplet excited state upon photo-excitation, or EL via a triplet exciton upon application of a DC voltage. These compounds according to one or more embodiments are highly soluble in common organic solvents, such as dichloromethane, chloroform, toluene and others. Alternatively, the compounds can be non-doped or doped into a host matrix for thin film preparation by either vacuum deposition, spin-coating, ink-jet printing or other known fabrication methods. In some embodiments, the compounds can be used for the fabrication of OLEDs as phosphorescent emitters or dopants to generate EL.
In an OLED according to one or more embodiments disclosed herein, the luminescent gold(III) compound is included in a light-emitting layer or emissive layer. The typical structure of an OLED using luminescent compounds of the present disclosure as a light-emitting layer or emissive layer is in the order shown in
Furthermore, a method for preparing luminescent gold(III) compounds with a triazine-containing cyclometalating tridentate ligand that exhibit TSDP properties and at least one aryl or alkynyl group, both coordinated to a gold(III) metal center is provided in one or more embodiments herein. The method includes a reaction according to:
in which:
Moreover, in one or more embodiments a light-emitting device with an ordered structure comprising an anode, a hole-transporting layer, a light-emitting layer, an electron-transporting layer and a cathode wherein the light-emitting layer comprises a gold(III) compound as disclosed herein. In one or more embodiments, the light-emitting layer or emissive layer is prepared using vacuum deposition or solution processing technique.
The disclosure is illustrated in the figures of the accompanying drawings which are meant to be exemplary and not limiting, in which like references are intended to refer to like or corresponding parts, and in which:
One aspect of the subject matter described herein is the novel concept of thermally stimulated delayed phosphorescence (TSDP) as well as the development of a new class of TSDP emitters, as exemplified by a novel class of tridentate-ligand containing luminescent gold(III) compounds with TSDP properties for applications in OLEDs. The gold(III) compounds are coordination compounds that contain one strong σ-donating group and one cyclometalating tridentate ligand, both coordinated to a gold(III) metal center. Other embodiments are directed to OLEDs based on this class of luminescent gold(III) compounds and methods related thereto. The TSDP compounds harvest light emission from the higher energy triplet excited state via the up-conversion from the lowest-energy triplet excited state by efficient spin-allowed reverse internal conversion.
The subject matter described herein provides another possible way to achieve blue emission from higher-lying triplet-excited state(s), in which the higher-energy blue phosphorescence is achieved via a novel mechanism termed as “thermally stimulated delayed phosphorescence (TSDP)”. This TSDP mechanism is unique and unprecedented but bears some similarities to that of TADF, where thermal up-conversion of excitons from lower energy excited states to higher energy excited states are observed. But instead of up-conversion via a spin-forbidden RISC from a triplet state to a singlet state, the excitons are found to be up-converted from the T1 state to the second lowest-energy triplet (T1′) state through the more efficient spin-allowed reverse internal conversion (RIC), as illustrated in
Specifically, for conventional blue triplet emitters, their emissive triplet (T1″) excited states are of such high energy that they are highly energetic and reactive and are more susceptible to photochemical decomposition and deactivation pathways, such as triplet-triplet annihilation, photochemical oxidative or reductive electron transfer, bond dissociation and degradation, etc. Such non-radiative photochemical decomposition and deactivation pathways not only would render the emitter a lower stability and a shorter lifetime, but also would compete with the emissive pathway, causing a decrease in the photoluminescence quantum yield (PLQY), as illustrated in pathway A of
Specifically, in conventional gold(III) emitters, as shown in pathway A of
In view of these, the introduction of the lower-lying less reactive T1 excited state as shown in
The present subject matter disclosed herein makes use of this TSDP mechanism to generate a new class of highly efficient triplet emitters, as exemplified by the gold(III) complexes for the fabrication of high performance OLEDs, while at the same time improving the photostability of the blue-emitting materials by incorporating a lower-lying lowest-energy triplet state to act as a buffer to minimize photodegradation of chemical bonds.
Further disclosed herein is the concept of using efficient spin-allowed RIC to achieve TSDP, and the design, synthesis and luminescence behavior of gold(III) complexes exhibiting TSDP properties and their application as phosphorescent dopants for the fabrication of both vacuum-deposited and solution-processable OLEDs. Notably, triplet excitons are harvested with higher energy from low-energy triplet excitons by up-conversion via RIC and the TSDP mechanism. Unlike most of the other platinum(II) and gold(III) systems, the luminescent gold(III) compounds of the present disclosure are unique and attractive in that they do not show excimer emission in the solid-state thin films and no significant spectral shift is observed upon an increase in dopant concentration. This TSDP property provides a new avenue for developing robust blue-emitting gold(III) compounds. In addition, the emission color of these gold(III) complexes can be readily tuned via the variation of different strong σ-donating groups. This new concept of using efficient spin-allowed RIC to achieve TSDP generates a new class of efficient TSDP emitters with high OLED performance, while at the same time allowing the improvement of the photostability of the blue emitting materials.
The luminescent gold(III) compounds with TSDP properties have the chemical structure shown in generic formula (I) and (II),
wherein:
In another embodiments, in the chemical structure shown in the generic formula (I), X and Y are carbon.
In another embodiments, in the chemical structure shown in the generic formula (I), A and B are unsubstituted or substituted phenyl groups, which may be substituted by 1, 2, or 3 substituents independently selected from halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, amino, nitro, hydroxyl, thio, halosulfanyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl.
In another embodiments, in the chemical structure shown in the generic formula (I), R1 is selected from, but not limited to, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocyclic, substituted heterocyclic, which may be substituted by 1, 2, 3, 4, or 5 substituents independently selected from halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, amino, nitro, hydroxyl, thio, halosulfanyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl.
In another embodiments, in the chemical structure shown in the generic formula (I), R2 is selected from, but not limited to, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocyclic, substituted heterocyclic, which may be substituted by 1, 2, or 3 substituents independently selected from halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, amino, nitro, hydroxyl, thio, halosulfanyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl.
In one or more embodiments, rings A and B are independently benzene, pyridine, phenyl and pyridyl derivatives, heterocycle or heterocyclic derivatives, but are not limited to, with one or more alkyl, alkenyl, alkynyl, aryl, cycloalkyl, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R, halo, aryl, substituted aryl, heteroaryl, substituted heteroaryl or heterocyclic group, wherein R is independently alkyl, alkenyl, alkynyl, alkyaryl, aryl, or cycloalkyl.
In the present disclosure the following terms are used.
The term “halo”, “halogen” or “halide” as used herein includes fluorine, chlorine, bromine and iodine.
The term “pseudohalide” as used herein includes, but not limited to, cyanate, thiocyanate and cyanide.
The term “alkyl” as used herein includes straight and branched chain alkyl groups, as well as cycloalkyl groups with alkyl groups having a cyclic structure. Preferred alkyl groups are those containing between one to eighteen carbon atoms (such as between one to twelve carbon atoms, between one to eight carbon atoms, or between one to six carbon atoms) and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and other similar compounds. In addition, the alkyl group may be optionally substituted with one or more substituents selected from OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R, halo and cyclic-amino, wherein R is independently alkyl, alkenyl, alkynyl, alkyaryl, aryl, or cycloalkyl.
The term “alkenyl” as used herein includes both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing between two and eighteen carbon atoms (such as between two to twelve carbon atoms, between two to eight carbon atoms, or between two to six carbon atoms). In addition, the alkenyl group may be optionally substituted with one or more substituents selected from OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R, halo and cyclic-amino, wherein R is independently alkyl, alkenyl, alkynyl, alkyaryl, aryl, or cycloalkyl.
The term “alkynyl” as used herein includes both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing between two and eighteen carbon atoms (such as between two to twelve carbon atoms, between two to eight carbon atoms, or between two to six carbon atoms). In addition, the alkynyl group may be optionally substituted with one or more substituents selected from OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R, halo and cyclic-amino, wherein R is independently alkyl, alkenyl, alkynyl, alkyaryl, aryl, or cycloalkyl.
“Alkoxy” refers to the group —OR wherein R is a substituted or unsubstituted alkyl as defined herein.
“Haloalkyl” refers to the above defined “alkyl”, which is substituted by one or more halo groups.
“Halosulfanyl” refers to a sulfanyl substituted by one or more halo groups, which includes —SF5.
“Cycloalkyl” refers to a radical of a non-aromatic cyclic hydrocarbon group having from 3 to 8 ring carbon atoms and zero heteroatoms.
The term “arylalkynyl” as used herein includes an alkynyl group which has an aromatic group as a substituent. In addition, the arylalkynyl group may be optionally substituted with one or more substituents selected from OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R, halo and cyclic-amino, wherein R is independently alkyl, alkenyl, alkynyl, alkyaryl, aryl, or cycloalkyl.
The term “alkylaryl” as used herein includes an aryl group which has an alkyl group as a substituent. In addition, the alkylaryl group may be optionally substituted with one or more substituents selected from OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R, halo and cyclic-amino, wherein R is independently alkyl, alkenyl, alkynyl, alkyaryl, aryl, or cycloalkyl.
The term “alkenylaryl” as used herein includes an aryl group which has an alkenyl group as a substituent. In addition, the alkenylaryl group may be optionally substituted with one or more substituents selected from OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R, halo and cyclic-amino, wherein R is independently alkyl, alkenyl, alkynyl, alkyaryl, aryl, or cycloalkyl.
The term “arylalkenyl” as used herein includes an aryl group which has an alkenyl unit as the point of attachment to the gold(III) metal center. In addition, the arylalkenyl group may be optionally substituted with one or more substituents selected from OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R, halo and cyclic-amino, wherein R is independently alkyl, alkenyl, alkynyl, alkyaryl, aryl, or cycloalkyl.
Aryl alone or in combination includes carbocyclic aromatic systems containing between six to eighteen carbon atoms (such as between six to twelve carbon atoms, between six to ten carbon atoms, or six carbon atoms). The systems may contain one, two or three rings wherein each ring may be attached together in a pendant manner or may be fused. Preferably the rings are 5- or 6-membered rings, such as phenyl. In one embodiment, the term substitute aryl includes substituted sulfanyl. In one embodiment, substituted sulfanyl includes pentafluorosulfanyl.
Heteroaryl alone or in combination includes heterocyclic aromatic systems containing between six to eighteen carbon atoms (such as between six to twelve carbon atoms, between six to ten carbon atoms, or six carbon atoms) and one to four heteroatoms independently selected from nitrogen, oxygen, and sulfur. The systems may contain one, two or three rings wherein each ring may be attached together in a pendant manner or may be fused. Preferably the rings are 5- or 6-membered rings.
Heterocyclic and heterocycle refer to a 3 to 7-membered ring containing at least one heteroatom. This includes aromatic rings including but not limited to pyridine, thiophene, furan, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, pyrrole, pyrazine, pyridazine, pyrimidine, benzimidazole, benzofuran, benzothiazole, indole, naphthalene, triazole, tetrazole, pyran, thiapyran, oxadiazole, triazine, tetrazine, carbazole, dibenzothiophene, dibenzofuran, fluorine, and non-aromatic rings including but not limited to piperazine, piperidine, and pyrrolidine. The groups of the present disclosure can be substituted or unsubstituted. Preferred substituents include but are not limited to alkyl, alkoxy, aryl.
Heteroatom refers to S, O, N, P, Se, Te, As, Sb, Bi, B, S1 and Ge.
Substituted refers to any level of substitution although mono-, di- and tri-substitutions are preferred. Preferred substituents include hydrogen, halogen, aryl, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, amino, nitro, hydroxyl, thio, halosulfanyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl.
Cyclometalating ligand is a term well known in the art and includes but is not limited to 2,6-diphenylpyridine (C{circumflex over ( )}N{circumflex over ( )}C), 2,6-bis(4-tert-butylphenyl)pyridine (tBuC{circumflex over ( )}N{circumflex over ( )}CtBu), 2,6-diphenyl-4-(2,5-difluorophenyl)pyridine (2,5-F2—C6H3—C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-p-tolylpyridine (C{circumflex over ( )}NTol{circumflex over ( )}C), 2,6-diphenyl-4-phenylpyridine (C{circumflex over ( )}NPh{circumflex over ( )}C), 2,6-bis(4-fluorophenyl)pyridine (FC{circumflex over ( )}N{circumflex over ( )}CF), 2,6-diphenyl-4-(4-isopropylphenyl)pyridine (4-iPr-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(4-nitrophenyl)pyridine (4-NO 2-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(4-methoxyphenyl)pyridine (4-OMe-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(4-methylyphenyl)pyridine (4-Me-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(4-ethylyphenyl)-pyridine (4-Et-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(2,3,4-trimethoxyphenyl)pyridine (2,3,4-OMe3-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-bis(4-methoxyphenyl)-4-(4-nitrophenyl)pyridine (4-NO 2-Ph-MeOC{circumflex over ( )}N{circumflex over ( )}COMe), 2,6-bis(2,4-dichlorophenyl)-4-(4-isopropylphenyl)-pyridine (4-iPr-Ph-C12C{circumflex over ( )}N{circumflex over ( )}CC12), 2,6-diphenyl-4-(4-tosylphenyl)pyridine (4-OTs-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(4-dimethylaminophenyl)pyridine (4-NMe2-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(4-diphenylaminophenyl)pyridine (4-NPh2-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(4-bromophenyl)pyridine (4-Br-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(4-chlorophenyl)pyridine (4-Cl-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(4-fluorphenyl)pyridine (4-F-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(4-iodophenyl)pyridine (4-I-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(2,5-dimethylphenyl)pyridine (2,5-Me2-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 2,6-diphenyl-4-(2,3,4,5,6-pentafluorophenyl)pyridine (2,3,4,5,6-F5-Ph-C{circumflex over ( )}N{circumflex over ( )}C), 1,3-diphenylisoquinoline (dpiq), 2,4,6-triphenyl-1,3,5-triazine (C{circumflex over ( )}NTRZ{circumflex over ( )}C), 2,4,6-tris(4-(tert-butyl)phenyl)-1,3,5-triazine (tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu).
Benzene includes substituted or unsubstituted benzene.
Pyridine includes substituted or unsubstituted pyridine.
Thiophene includes substituted or unsubstituted thiophene.
Furan includes substituted or unsubstituted furan.
Pyrazole includes substituted or unsubstituted pyrazole.
Imidazole includes substituted or unsubstituted imidazole.
Oxazole includes substituted or unsubstituted oxazole.
Isoxazole includes substituted or unsubstituted isoxazole.
Thiazole includes substituted or unsubstituted thiazole.
Isothiazole includes substituted or unsubstituted isothiazole.
Pyrrole includes substituted or unsubstituted pyrrole.
Pyrazine includes substituted or unsubstituted pyrazine.
Pyridazine includes substituted or unsubstituted pyridazine.
Pyrimidine includes substituted or unsubstituted pyrimidine.
Benzimidazole includes substituted or unsubstituted benzimidazole.
Benzofuran includes substituted or unsubstituted benzofuran.
Benzothiazole includes substituted or unsubstituted benzothiazole.
Indole includes substituted or unsubstituted indole.
Naphthalene includes substituted or unsubstituted naphthalene.
Triazole includes substituted or unsubstituted triazole.
Tetrazole includes substituted or unsubstituted tetrazole.
Pyran includes substituted or unsubstituted pyran.
Thiapyran includes substituted or unsubstituted thiapyran.
Oxadiazole includes substituted or unsubstituted oxadiazole.
Triazine includes substituted or unsubstituted triazine.
Tetrazine includes substituted or unsubstituted tetrazine.
Carbazole includes substituted or unsubstituted carbazole.
Dibenzothiophene includes substituted or unsubstituted dibenzothiophene.
Dibenzofuran includes substituted or unsubstituted dibenzofuran.
Piperazine includes substituted or unsubstituted piperazine.
Piperidine includes substituted or unsubstituted piperidine.
Pyrrolidine includes substituted or unsubstituted pyrrolidine.
In some embodiments, the luminescent gold(III) compounds of general structures (I) are prepared in high purity. The compounds described have been represented throughout by their monomeric structure. As is well known to those skilled in the art, the compounds may also be present as dimers, trimers or dendrimers.
While the gold(III) compounds described herein are described with use in OLEDs, the compounds have additional applications as would be understood to those who are skilled in the art. The gold(III) compounds described herein have strong light emitting and light absorption properties that make them suitable for inclusion into common apparatuses for which light emission or absorption are desired. For example, the gold(III) compounds may be used as, but are not limited to, the backlighting of flat panel displays of wall-mounted televisions, copiers, printers, liquid crystal displays, measuring instruments, display boards, marker lamps, electrophotographic photoreceptors, photoelectric transducers, solar cells and image sensors.
The luminescent gold(III) compounds can be used to form thin films by vacuum deposition, spin-coating, ink-jet printing or other known fabrication methods and be applied in OLEDs. A typical OLED has, in order, substrate, hole-injecting anode, hole transporting layer, light-emitting layer, electron transporting layer, and electron-injecting cathode. In general, the emissive layer is sandwiched between the hole-transporting layer and the electron-transporting layer. To ensure an efficient exothermic energy transfer between the host material and the dopant material, the triplet energy of the host material must be larger than that of the dopant material. In addition, both the ionization potential and the electron affinity of the host material should be larger than those of the dopant material in order to achieve efficient Förster energy transfer from the host to the dopant. In order to confine triplet excitons within the emissive layer, the triplet energy of the hole-transporting material and electron-transporting material should be larger than that of the dopant material.
With reference now to
The cathode 310 and anode 350 are a pair of electrodes sandwiching these plurality of semiconductor layers that cause EL when voltage is applied to the OLED 300. The cathode 310 acts as a transmissive electron injector that injects electrons into the organic emissive layer 130 when the cathode is negatively biased. The cathode comprises a thin fluoride layer (which may be omitted) and a metal or metal alloy, preferably having a work function of less than 4 eV. The cathode 310 may be made of suitable materials such as, for example, Mg:Ag, Ca, Li:Al, Al, or Ba. The anode 350 injects holes into the emissive layer when the anode is positively biased. The anode 350 is composed of a conductive and optionally transmissive layer. In one or more embodiments, viewing the emissive layer 130 through the substrate 360 is desirable, and the anode is transparent. In other embodiments, the emissive layer 130 is viewed through the top electrode and the transmissive characteristics of anode 350 are immaterial, and therefore any appropriate materials including metals or metal compounds having a work function of greater than 4.1 eV may be used. For example, appropriate metals include silver, gold, iridium, nickel, molybdenum, palladium, and platinum. In one or more embodiments, the anode 350 is transmissive, and suitable materials are metal oxides, including indium-tin oxide, aluminum- or indium-doped zinc oxide, tin oxide, magnesium-indium oxide, nickel-tungsten oxide, and cadmium-tin oxide. The preferred metals and metal oxides can be deposited by evaporation, sputtering, laser ablation, and chemical vapor deposition. The cathode 310 and anode 350 can have thicknesses between 100-200 nm.
In one or more embodiments, the anode 350 layer is positioned on top of a substrate 360. The substrate 360 is electrically insulated and is used to emit the light created by the OLED 300, in which it is typically made of optically transparent material. For example, the substrate 360 can be made of glass, plastic foil, or a transparent polymer. In one or more alternative embodiments, the substrate is opaque and comprises one or more semiconducting materials or ceramics. In one embodiment, the emissive layer 330 is viewed through the substrate 360, or through both sides of the device, and substrate comprises a transparent glass substrate or a plastic foil. In other embodiments, the emissive layer 330 is viewed only through the top electrode, and substrate 360 comprises an opaque semiconductor or ceramic wafers.
The ETL 320 provides high electron affinity and high electron mobility to the OLED 300 for electrons to flow across the various OLED layers. To do this, the electron-transporting layer 120 includes materials or mixtures of materials having a high ionization potential and wide optical band gap. In one or more embodiments, the ETL 320 has a thickness between 30-80 nm. In one or more embodiments, additional electron transporting materials are added to ETL 320 to facilitate electron emission. The materials for the ETL 320 are selected to maximize OLED efficiency. As some non-limiting examples, suitable electron-transporting materials include but not limited to 1,3,5-tris(phenyl-2-benzimidazolyl)-benzene (TPBI), 1,3,5-tri[(3-pyridyl)-phen-3-yl] benzene (TmPyPB), bathocuproine (BCP), bathophenanthroline (BPhen) and bis(2-methyl-8-quinolinolate)-4-(phenylphenolate)aluminum (B Alq), tris-[2,4,6-trimethyl-3-(pyridin-3-yl)phenyl]borane (3TPYMB), and 1,3-bis[3,5-di(pyridin-3-yl)phenyl]benzene (BmPyPhB). In one embodiment, the electron-transporting layer 120 is prepared as an organic film by thermal evaporation, spin-coating, ink-jet printing from a solution, or other known fabrication methods.
Light-emitting layer or emissive layer 330 in
In general, the emissive layer 330 is sandwiched between the hole-transporting layer 340 and the electron-transporting layer 320. To ensure an efficient exothermic energy transfer between the host material and the dopant material, the triplet energy of the host material must be larger than that of the dopant material. In addition, both the ionization potential and the electron affinity of the host material should be larger than those of the dopant material in order to achieve efficient Förster energy transfer from the host to the dopant. In order to confine triplet excitons within the emissive layer, the triplet energy of the hole-transporting material and electron-transporting material should be larger than that of the dopant material.
The HTL 340 is layered on top of the anode 350 and plays a role in the adjustment of electron/hole injection to attain transport balance of charge carriers in the emissive layer 130 of the OLED 300. In one or more embodiments, the HTL 340 has a thickness between 30-80 nm. The materials for the HTL 340 are selected to maximize OLED efficiency. As some non-limiting examples, the HTL 340 can include, but not limited to, polycyclic aromatic compounds, for example, 4,4′-bis [N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), 4,4′-bis [N-(3-methylphenyl)-N-phenylamino]biphenyl (TPD), 4,4′,4′-tris[(3-methylphenyl)phenylamino] triphenylamine (MTDATA), and di-[4-(N,N-ditolyl-amino)phenyl] cyclohexane (TAPC). In addition, polymeric hole-transporting materials can be used including PVK, polythiophene, polypyrrole, polyaniline, and copolymers including poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS).
In some embodiments, novel luminescent gold(III) compounds are either the primary luminescent material or a secondary luminescent material in device. In some embodiments, the gold(III) compounds are employed as electrophosphorescent dopants in multilayer OLEDs with EQEs of up to 7.7%. The novel TSDP mechanism disclosed herein allows thermal up-conversion of triplet excitons, generating blue emission having high color purity. In addition, the gold(III) compounds disclosed herein can be deposited to form thin films by either vacuum deposition, spin-coating, screen printing or ink-jet printing. Their high solubilities in a variety of organic solvents also permits simple and economic manufacturing and patterning of large-area displays.
The present disclosure will be illustrated more specifically by the following non-limiting examples, it being understood that changes and variations can be made therein without deviating from the scope and the spirit of the disclosure as hereinafter claimed. It is also understood that various theories as to why the disclosure works are not intended to be limiting.
Throughout the following examples, reference is made to
General Synthetic Methodology:
wherein:
The tridentate ligand, 2,4,6-tris(4-(tert-butyl)phenyl)-1,3,5-triazine, 2,4,6-tris(2-methoxyphenyl)-1,3,5-triazine, 2,6-bis(4-(tert-butyl)phenyl)pyrazine and 2,6-bis(4-(tert-butyl)phenyl)pyridine, and the precursor compound, [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBU){circumflex over ( )}CtBu}Cl], [Au{(2-MeO)-C{circumflex over ( )}NTRZ(C6H4-2-OMe){circumflex over ( )}C-(2-OMe)}Cl], [Au{tBuC{circumflex over ( )}Npz{circumflex over ( )}CtBu}Cl] and [Au{tBuC{circumflex over ( )}N{circumflex over ( )}CtBu}Cl] were prepared according to modification of procedures reported in the literature [Wong, K.-H.; Cheung, K.-K.; Chan, M. C.-W.; Che, C.-M. Organometallics 17, 3505 (1998); Tanaka, H.; Shizu, K.; Nakanotani, H.; Adachi, C. J. Phys. Chem. C 118, 15985 (2014)]. The target compounds were synthesized according to a procedure reported in the literature with modification [Tang, M.-C.; Lee, C.-H.; Lai, S.-L.; Ng, M.; Chan, M.-Y.; Yam, V. W.-W. J. Am. Chem. Soc. 139, 9341 (2017)]. For example, compound 1 was synthesized by stirring a mixture of [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}Cl] (200 mg, 0.28 mmol), K2CO3 (276 mg, 2.0 mmol), Pd(OAc)2 (6 mg, 0.028 mmol), [HP(tBu)3]BF4 (16 mg, 0.056 mmol), and the corresponding boronic acid (0.56 mmol) in degassed tetrahydrofuran-H2O (45 mL, 8:1, v/v) at 80° C. for 12 h under a nitrogen atmosphere, followed by column chromatography to yield a yellow solid. The product was further purified by dissolving in dichloromethane and layering with methanol. The solid was filtered and dried under vacuum to give a yellow solid (152 mg). Compounds 2-24 were synthesized using similar procedure as compound 1.
1H NMR spectra were recorded on a Bruker AVANCE 500 or 600 (500 MHz, 600 MHz) Fourier-transform NMR spectrometer with chemical shifts reported relative to tetramethylsilane (δ 0 ppm). 19F{1H}NMR spectra were recorded on a Bruker AVANCE 400 (162 MHz) Fourier-transform NMR spectrometer with chemical shifts reported relative to trifluoroacetic acid (δ=−76.55 ppm) in chloroform. The results of the analyses confirm the high purity of compounds 1-24.
The characterization data of compounds 1-24 are as set forth in the subsequent paragraphs.
Compound 1: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBU){circumflex over ( )}CtBu}(C6H4-tBu-4)]. Yield: 152 mg, 67%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me 4 S1, δ/ppm): δ 8.68 (d, J=8.5 Hz, 2H), 8.20 (d, J=8.0 Hz, 2H), 7.75 (d, J=2.0 Hz, 2H), 7.66 (d, J=8.0 Hz, 2H), 7.62 (d, J=8.5 Hz, 2H), 7.42 (dd, J=8.5, 2.0 Hz, 2H), 7.39 (d, J=8.5 Hz, 2H), 1.41 (s, 18H), 1.32 (s, 18H). HRMS (positive ESI) found 806.3783 [M+H]+; calcd for C43H50N3Au (m/z) 806.3743.
Compound 2: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(C6H4—CF3-4)]. Yield: 143 mg, 62%. 1H NMR (600 MHz, CDCl3, 298 K, relative to Me 4 S1, δ/ppm): δ 8.68 (d, J=8.4 Hz, 2H), 8.19 (d, J=8.1 Hz, 2H), 7.84 (d, J=7.9 Hz, 2H), 7.63 (d, J=8.4 Hz, 2H), 7.59 (d, J=8.1 Hz, 2H), 7.56 (d, J=1.6 Hz, 2H), 7.43 (dd, J=8.1, 1.6 Hz, 2H), 1.42 (s, 9H), 1.30 (s, 18H). 19F{1H} NMR (376 MHz, CDCl3, 298 K, relative to CF3COOH, δ/ppm) δ 61.95. HRMS (positive ESI) found 818.2961 [M+H]+; calcd for C40H41AuF3N3 (m/z) 818.2991.
Compound 3: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(C6H3—F2-3,5)]. Yield: 135 mg, 61%. 1H NMR (600 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.67 (d, J=8.5 Hz, 2H), 8.18 (d, J=8.2 Hz, 2H), 7.62 (d, J=8.5 Hz, 2H), 7.60 (d, J=1.8 Hz, 2H), 7.44 (dd, J=8.2, 1.8 Hz, 2H), 7.26-7.27 (m, 2H), 6.72-6.76 (m, 2H), 1.42 (s, 9H), 1.32 (m, 18H). 19F{1H} NMR (376 MHz, CDCl3, 298 K, relative to CF 3 COOH, δ/ppm) δ 108.73. HRMS (positive ESI) found 786.2902 [M+H]+; calcd for C39H40AuF2N3 (m/z) 786.2929.
Compound 4: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(C6H2—F3-3,4,5)]. Yield: 115 mg, 51%. 1H NMR (600 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.68 (d, J=10.2 Hz, 2H), 8.19 (d, J=10.2 Hz, 2H), 7.63 (d, J=10.2 Hz, 2H), 7.57 (d, J=1.8 Hz, 2H), 7.45 (dd, J=10.2, 1.8 Hz, 2H), 7.35 (d, J=9 Hz, 2H), 1.42 (s, 9H), 1.33 (s, 18H). 19F{1H} NMR (376 MHz, CDCl3, 298 K, relative to CF3COOH, δ/ppm) δ 166.43, 137.60. HRMS (positive ESI) found 804.2822 [M+H]+; calcd for C39H39AuF3N3 (m/z) 804.2835.
Compound 5: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(C6F5)]. Yield: 113 mg, 48%. 1H NMR (600 MHz, CDCl3, 298 K, relative to Me 4 S1, δ/ppm): δ 8.68 (d, J=10.2 Hz, 2H), 8.17 (d, J=9.6 Hz, 2H), 7.63 (d, J=10.2 Hz, 2H), 7.44 (dd, J=1.8, 10.2 Hz, 2H), 7.39 (dd, J=1.8, 9.6 Hz, 2H), 1.42 (s, 9H), 1.29 (s, 18H). 19F{1H} NMR (376 MHz, CDCl3, 298 K, relative to CF3COOH, δ/ppm) δ 162.06, 158.17, 119.12. HRMS (positive ESI) found 840.2633 [M+H]+; calcd for C39H37AuF5N3 (m/z) 840.2646.
Compound 6: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBU){circumflex over ( )}CtBU}(C6H4—SF5-4)]. Yield: 132 mg, 54%. 1H NMR (600 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.68 (d, J=10.2 Hz, 2H), 8.20 (d, J=9.8 Hz, 2H), 7.82 (d, J=9.8 Hz, 2H), 7.72 (d, J=10.4 Hz, 2H), 7.63 (d, J=10.2 Hz, 2H), 7.53 (d, J=2.2 Hz, 2H), 7.44 (dd, J=2.2, 10.4 Hz, 2H), 1.42 (s, 9H), 1.30 (s, 18H). HRMS (positive ESI) found 876.2646 [M+H]+; calcd for C39H41AuF5N3S (m/z) 876.2680.
Compound 7: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}{C6H4—Si—(C6H5)4-4}]. Yield: 138 mg, 49%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.68 (d, J=8.5 Hz, 2H), 8.20 (d, J=8.2 Hz, 2H), 7.75 (d, J=7.7 Hz, 2H), 7.61-7.70 (m, 8H), 7.54 (d, J=7.7 Hz, 2H), 7.39-7.47 (m, 13H), 1.41 (s, 9H), 1.32 (s, 18H).
Compound 8: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(C6H4—OCH3-4)]. Yield: 115 mg, 51%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.68 (d, J=8.6 Hz, 2H), 8.20 (d, J=8.1 Hz, 2H), 7.73 (d, J=1.9 Hz, 2H), 7.66 (d, J=8.7 Hz, 2H), 7.62 (d, J=8.6 Hz, 2H), 7.43 (d, J=8.2 Hz, 2H), 6.97 (d, J=8.7 Hz, 2H), 3.9 (s, 3H), 1.41 (s, 9H), 1.32 (s, 18H). HRMS (positive ESI) found 708.3217 [M+H]+; calcd for C51H49AuN4 (m/z) 780.3222.
Compound 9: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(C6H4-9H-cbz-4)]. Yield: 73 mg, 31%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.71 (d, J=6.5 Hz, 2H), 8.25 (d, J=8.0 Hz, 2H), 8.20 (d, J=7.5 Hz, 2H), 7.99 (d, J=8.5 Hz, 2H), 7.78 (d, J=2.0 Hz, 2H), 7.65 (d, J=8.5 Hz, 2H), 7.58 (t, J=8.5 Hz, 2H), 7.44-7.48 (m, 4H), 7.30-7.33 (m, 2H), 1.43 (s, 9H), 1.35 (s, 18H). HRMS (positive ESI) found 915.3667 [M+H]+; calcd for C51H49AuN4 (m/z) 915.3696.
Compound 10: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(3-9H-cbz-CH3-9)]. Yield: 143 mg, 60%. 1H NMR (600 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.70 (d, J=10.2 Hz, 2H), 8.38 (s, 1H), 8.24 (d, J=9.6 Hz, 2H), 8.08 (d, J=9.6 Hz, 1H), 7.90 (d, J=10.2 Hz, 1H), 7.84 (d, J=1.8 Hz, 1H), 7.63 (d, J=10.2 Hz, 2H), 7.50-7.42 (m, 5H), 7.26-7.20 (m, 2H), 1.42 (s, 9H), 1.28 (s, 18H). HRMS (positive ESI) found 853.3511 [M+H]+; calcd for C46H47AuN4 (m/z) 853.3539.
Compound 11: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(3-9H-cbz-C12H25-9)]. Yield: 175 mg, 62%. 1H NMR (600 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.71 (d, J=10.2 Hz, 2H), 8.38 (s, 1H), 8.24 (d, J=9.6 Hz, 2H), 8.08 (d, J=9.6 Hz, 1H), 7.89-7.86 (m, 3H), 7.63 (d, J=10.2 Hz, 2H), 7.63 (d, J=10.2 Hz, 2H), 7.47-7.43 (m, 5H), 7.22-7.17 (m, 2H), 1.99-1.91 (m, 2H), 1.49-1.34 (m, 18H), 1.29-1.26 (m, 27H), 0.88-0.86 (m, 3H). HRMS (positive ESI) found 1007.5172 [M+H]+; calcd for C45H45AuN4 (m/z) 1007.5261.
Compound 12: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(9-9H-cbz)]. Yield: 164 mg, 71%. 1H NMR (600 MHz, CDCl3, 298 K, relative to Me 4 S1, δ/ppm): δ 8.71 (d, J=10.2 Hz, 2H), 8.22 (d, J=9 Hz, 2H), 8.16 (d, J=9.6 Hz, 1H), 7.66 (d, J=10.2 Hz, 1H), 7.51 (d, J=9.6 Hz, 1H), 7.41-7.39 (m, 2H), 7.31-7.26 (m, 4H), 7.15 (t, J=9 Hz, 2H), 1.43 (s, 9H), 1.04 (s, 18H). HRMS (positive ESI) found 839.3366 [M+H]+; calcd for C45H45AuN4 (m/z) 839.3382.
Compound 13: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(9-9H-cbz-tBu2-3,6)]. Yield: 135 mg, 55%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.71 (d, J=8.5 Hz, 2H), 8.19 (s, 2H), 8.14 (d, J=8.0 Hz, 2H), 7.65 (d, J=7.5 Hz, 2H), 7.38-7.42 (m, 4H), 7.33-7.35 (m, 4H), 1.47 (s, 18H), 1.43 (s, 9H), 1.05 (s, 18H). HRMS (positive ESI) found 950.4538 [M+H]+; calcd for C53H62AuN4 (m/z) 950.4556.
Compound 14: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(C≡CC6H4-tBu-4)]. Yield: 90 mg, 42%. 1H NMR (400 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.65 (d, J=9.0 Hz, 2H), 8.31 (d, J=2.0 Hz, 2H), 8.10 (d, J=8.0 Hz, 2H), 7.56-7.62 (m, 4H), 7.45 (dd, J=8.0, 2.0 Hz, 2H), 7.39 (d, J=8.6 Hz, 2H), 1.40-1.41 (m, 27H), 1.37 (s, 9H). HRMS (positive ESI) found 830.3786 [M+H]+; calcd for C40H45AuN30 (m/z) 830.3743.
Compound 15: [Au{tBuC{circumflex over ( )}NTRZ(C6H4-tBu){circumflex over ( )}CtBu}(S—C6H4—CH3-4)]. Yield: 123 mg, 60%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.67 (d, J=8.7 Hz, 2H), 8.15 (d, J=8.1 Hz, 2H), 7.61-7.65 (m, 4H), 7.42 (d, J=1.7 Hz, 2H), 7.38 (d, J=8.1 Hz, 4H), 7.07 (d, J=7.9 Hz, 2H), 2.34 (s, 3H), 1.41 (s, 9H), 1.23 (s, 18H). HRMS (positive ESI) found 795.2867 [M]+; calcd for C40H44AuN3S (m/z) 795.2916.
Compound 16: [Au{MeO-C{circumflex over ( )}NTRZ(C6H4—OMe){circumflex over ( )}C—OMe}(C6H4-tBu-4)]. Yield: 116 mg, 57%. 1H NMR (600 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.43 (dd, J=9, 1.8 Hz, 1H), 7.57-7.54 (m, 3H), 7.48 (t, J=9.0 Hz, 2H), 7.33 (d, J=9.6 Hz, 2H), 7.32-7.01 (m, 4H), 6.87 (d, J=10.2 Hz, 2H), 4.06 (s, 3H), 4.06 (s, 6H), 1.39 (s, 18H). HRMS (positive ESI) found 728.2167 [M+H]+; calcd for C34H32AuO3N3 (m/z) 728.2182.
Compound 17: [Au{MeO—C{circumflex over ( )}NTRZ(C6H4—OMe){circumflex over ( )}C—OMe}(C6H4—CF3-4)]. Yield: 109 mg, 55%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.45-8.43 (m, 1H), 7.59-7.55 (m, 1H), 7.50-7.47 (m, 2H), 7.19-7.11 (m, 4H), 7.00 (d, J=8.4 Hz, 2H), 6.90 (d, J=10.2 Hz, 2H), 6.72-6.68 (m, 1H), 4.07 (s, 3H), 4.05 (s, 6H). HRMS (positive ESI) found 708.1343 [M+H]+; calcd for C30H22AuF2N3O3 (m/z) 708.1368.
Compound 18: [Au{tBuC{circumflex over ( )}Npz{circumflex over ( )}CtBu}(C6H5-4)]. Yield: 104 mg, 55%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.86 (s, 2H), 7.67 (d, J=8.2 Hz, 2H), 7.47-7.60 (m, 4H), 7.36 (d, J=8.4 Hz, 2H), 7.30 (dd, J=8.2, 2.0 Hz, 2H), 1.27 (s, 18H). HRMS (positive ESI) found 673.2879 [M+H]+; calcd for C34H40AuN2 (m/z) 673.2857.
Compound 19: [Au{tBuC{circumflex over ( )}Npz{circumflex over ( )}CtBu}(C6H4-9H-cbz-4)]. Yield: 79 mg, 36%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.90 (s, 2H), 8.18 (d, J=7.8 Hz, 2H), 7.92 (d, J=8.4 Hz, 2H), 7.71 (d, J=8.2 Hz, 2H), 7.61 (d, J=2.0 Hz, 2H), 7.52-7.56 (m, 4H), 7.45-7.47 (m, 2H), 7.29-7.44 (m, 4H), 1.31 (s, 18H). HRMS (positive ESI) found 782.2774 [M+H]+; calcd for C42H39AuN3 (m/z) 782.2804.
Compound 20: [Au{tBuC{circumflex over ( )}Npz{circumflex over ( )}CtBu}(3-9H-cbz-CH3-9)]. Yield: 87 mg, 43%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me 4 S1, δ/ppm): δ 8.88 (s, 2H), 8.44 (s, 1H), 8.05 (d, J=7.7 Hz, 1H), 7.83 (dd, J=8.3, 1.3 Hz, 1H), 7.68-7.71 (m, 4H), 7.43-7.49 (m, 3H), 7.31 (dd, J=8.1, 2.0 Hz, 2H), 7.19-7.22 (m, 1H), 3.93 (s, 3H), 1.23 (s, 18H). HRMS (positive ESI) found 720.2621 [M+H]+; calcd for C37H37AuN3 (m/z) 720.2648.
Compound 21: [Au{tBuC{circumflex over ( )}Npz{circumflex over ( )}CtBu}(9-9H-cbz)]. Yield: 119 mg, 60%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.83 (s, 2H), 8.20 (d, J=7.8 Hz, 2H), 7.64 (d, J=8.2 Hz, 2H), 7.48 (d, J=8.2 Hz, 2H), 7.27-7.30 (m, 4H), 7.12-7.15 (m, 2H), 7.06 (d, J=1.9 Hz, 2H), 0.99 (s, 18H). HRMS (positive ESI) found 706.2444 [M+H]+; calcd for C36H35AuN3 (m/z) 706.2491.
Compound 22: [Au{tBuC{circumflex over ( )}Npz{circumflex over ( )}CtBu}(9-9H-cbz-tBu2-3,6)]. Yield: 117 mg, 51%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.81 (s, 2H), 8.17 (d, J=1.7 Hz, 2H), 7.62 (d, J=8.2 Hz, 2H), 7.37 (d, J=8.6 Hz, 2H), 7.32 (dd, J=8.6, 1.9 Hz, 2H), 7.25-7.27 (m, 4H), 7.13 (d, J=1.9 Hz, 2H), 1.46 (s, 18H), 0.99 (s, 18H). HRMS (positive ESI) found 818.3722 [M+H]+; calcd for C44H51AuN3 (m/z) 818.3739.
Compound 23: [Au{tBuC{circumflex over ( )}Npz{circumflex over ( )}CtBu}(C≡CC6H4-tBu-4)]. Yield: 90 mg, 42%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.70 (s, 2H), 8.16 (d, J=2.0 Hz, 2H), 7.51-7.55 (m, 4H), 7.38 (d, J=8.5 Hz, 2H), 7.27 (dd, J=8.5, 2.0 Hz, 2H), 1.38 (s, 18H), 1.36 (s, 9H). HRMS (positive ESI) found 697.2801 [M+H]+; calcd for C36H40AuN2 (m/z) 697.2852.
Compound 24: [Au{tBuC{circumflex over ( )}N{circumflex over ( )}C t Bu}(C6H4-9H-cbz-4)]. Yield: 163 mg, 68%. 1H NMR (500 MHz, CDCl3, 298 K, relative to Me4S1, δ/ppm): δ 8.18 (d, J=7.8 Hz, 2H), 7.94 (d, J=8.2 Hz, 2H), 7.85 (t, J=8.0 Hz, 1H), 7.60-7.62 (m, 6H), 7.50-7.59 (m, 6H), 7.43-7.47 (m, 2H), 7.39-7.31 (m, 4H), 1.30 (s, 18H). HRMS (positive ESI) found 780.2741 [M]+; calcd for C43H39AuN2 (m/z) 780.2773.
The UV-vis absorption spectra of representative compounds 1-3 as disclosed in
[a]The relative luminescence quantum yield in solution was measured at room temperature using quinine sulfate in 0.5M H2SO4 as the reference (excitation wavelength = 365 nm, Φlum = 0.546)
[b]Absolute luminescence quantum yield of thin films was measured with 320 nm excitation
As shown by TABLE 1, representative compounds 1-3 display yellow luminescence in solution state. The emission spectra in degassed dichloromethane solution are shown in
To confirm the occurrence of the TSDP mechanism, temperature-dependent emission properties of the gold(III) compounds in solid state were investigated and compounds 1-3 are used for exemplary illustration. The emission spectra of compounds 1 and 2 in the solid state at different temperatures from 180 K to 300 K, and that of compound 3 from 77 K to 300 K are shown in
An exemplary vacuum-deposited OLED according to an embodiment was constructed in the following manner.
A transparent anode ITO-coated borosilicate glass substrate (38 mm×38 mm) with sheet resistance of 30Ω per square was ultrasonicated in the commercial detergent Decon 90, rinsed in deionized water having a resistivity of 18.2 mega-ohm for 15 minutes, and then dried in an oven at 120 degree C. for at least an hour. The substrate was next subjected to an UV-ozone treatment in a Jelight 42-220 UVO-Cleaner equipped with a mercury grid lamp for 15 minutes in order to increase the work function of the ITO-coated glass substrate for better hole injection into the organic layer.
The substrate was put into a vacuum chamber, and the chamber was pumped down from 1 bar to 5×10−6 mbar.
A 40-nm thick α-NPD hole-blocking layer was deposited by thermal evaporation onto the doped light-emitting layer of step b.
A 25-nm thick light-emitting layer was deposited by thermal evaporation onto the α-NPD layer of step c, in which compound 1 was doped into a 2,6-di(9H-carbazol-9-yl)pyridine (PYD-2Cz) host at different concentrations in the range from 2 to 14 wt %.
A 5-nm thick diphenyl-4-triphenylsilylphenyl-phosphine oxide (TSPO1) hole-blocking layer was deposited by thermal evaporation onto the doped light-emitting layer of step d.
A 35-nm thick 1,3,5-tris(6-(3-(pyridine-3-yl)phenyl)pyridine-2-yl)benzene (Tm3Py26PyB) electron-transporting layer was deposited by thermal evaporation onto the TSPO1 layer of step e.
A 1-nm thick LiF layer and a 150-nm thick Al layer were deposited by thermal evaporation onto the Tm3Py26PyB layer of step f to form an electron-injecting cathode.
α-NPD, TSPO1, Tm3Py26PyB, LiF and Al were prepared by thermal evaporation from tantalum boats by applying current through the tantalum boats. Deposition rates were monitored with a quartz oscillation crystal and controlled at 0.1-0.2 nm s−1 for both organic and metal layers. Current density-voltage-luminance characteristics of organic EL devices were measured with a programmable Keithley model 2420 power source and a Spectrascan PR-655 colorimeter under ambient air conditions.
The same materials and processing procedures were employed as described in Example 5, except that compound 2 was doped into PYD-2Cz as the light-emitting layer.
The same materials and processing procedures were employed as described in Example 5, except that compound 3 was doped into PYD-2Cz as the light-emitting layer.
As depicted in
Similar to the case of compound 1, the emission energies in the EL spectra are almost identical to the PL spectra in thin film for both compounds 2 and 3, demonstrating an identical emission origin. Also, the host emission is not observed, indicating a complete energy transfer to the dopant. In particular, nice blue emission with peak maxima at ca. 484 nm can be realized for both devices and CIE x and y coordinates of approximately (0.17, (
Solution-processable OLEDs according to an embodiment were constructed in the following manner.
A transparent anode ITO-coated borosilicate glass substrate (38 mm×38 mm) with sheet resistance of 30Ω per square was ultrasonicated in the commercial detergent Decon 90, rinsed in deionized water having a resistivity of 18.2 mega-ohm for 15 minutes, and then dried in an oven at 120 degree C. for at least an hour. The substrate was next subjected to an UV-ozone treatment in a Jelight 42-220 UVO-Cleaner equipped with a mercury grid lamp for 15 minutes in order to increase the work function of the ITO-coated glass substrate for better hole injection into the organic layer.
A 70-nm thick PEDOT:PSS hole-transporting layer was spin-coated by using a spin processor at 7000 rpm for 30 seconds onto the ITO-coated glass substrate of step a and baked at 100 degree C. for 10 minutes in air.
A 60-nm thick light-emitting layer was spin-coated by using a spin processor at 6000 rpm for 25 seconds onto PEDOT:PSS layer of step b, and baked at 80 degree C. for minutes in air, in which compound 1 was doped into PYD-Cz2 host at different concentrations in the range from 5 to 20 wt %.
The substrate was put into a vacuum chamber, and the chamber was pumped down from 1 bar to 5×10−6 mbar.
A 30-nm thick 3TPyMB hole-blocking layer was deposited by thermal evaporation onto the doped light-emitting layer of step c.
A 30-nm thick TmPyPB electron-transporting layer was deposited by thermal evaporation onto the 3TPyMB layer of step e.
A 1-nm thick LiF layer and a 120-nm thick Al layer were deposited by thermal evaporation onto the TmPyPB layer of step f to form an electron-injecting cathode.
3TPyMB, TmPyPB, LiF and Al were prepared by thermal evaporation from tantalum boats by applying current through the tantalum boats. Deposition rates were monitored with a quartz oscillation crystal and controlled at 0.1-0.2 nm s−1 for both organic and metal layers. Current density-voltage-luminance characteristics of organic EL devices were measured with a programmable Keithley model 2420 power source and a Spectrascan PR-655 colorimeter under ambient air conditions.
The same materials and processing procedures were employed as described in Example 8, except that compound 2 was doped into PYD-2Cz as the light-emitting layer.
The same materials and processing procedures were employed as described in Example 8, except that compound 3 was doped into PYD-2Cz as the light-emitting layer.
This application is a Divisional application of U.S. application Ser. No. 16/959,462, filed on Jul. 1, 2020, which is a U.S. National Stage Application under 35 U.S.C. § 371 of International Patent Application No. PCT/CN2019/070126, filed Jan. 2, 2019, which claims the benefit of priority of U.S. Patent Application No. 62/612,792 filed Jan. 2, 2018, each of which are incorporated by reference in their entireties. The International Application was published on Jul. 11, 2019, as International Publication No. WO 2019/134651 A1.
| Number | Date | Country | |
|---|---|---|---|
| 62612792 | Jan 2018 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16959462 | Jul 2020 | US |
| Child | 18451432 | US |
