Transition metal luminescent complexes and methods of use

Abstract

The invention relates to transition metal luminescent complexes and methods of use. Described herein are transition metal complexes containing nickel (II) and tridentate and tetradentate ligands as central metal atoms. The transition metal complexes also include auxiliary ligands having strong sigma-giving properties. The auxiliary ligand enhances luminescence by increasing the opportunity of filling in the emission state. The transition metal complexes emit at room temperature and / or low temperature in various media so that they can be used as luminescent materials for OLEDs.

Description

[0001] This application is a divisional application of an invention patent application. The application date of the parent application is December 4, 2019, the application number is 201911226312.3, and the name of the invention is "Transition metal luminescent complexes and methods of use". Field of the Invention

[0002] The disclosed invention is generally in the field of transition metal luminescent complexes, in particular luminescent nickel(II) complexes containing cyclometalated tridentate and tetradentate ligands, and their use in organic light emitting devices (OLEDs). Background of the Invention Transition metal complexes have gained great interest as molecular probes, catalysts, and luminescent materials in both commercial and academic settings. As luminescent materials, transition metal complexes are increasingly being explored as potential alternatives to purely organic-based materials due to their potential to improve luminescence efficiency compared to purely organic-based materials.

[0004] Flat square d 8Platinum (II) complexes have been recognized as one of the most important classes of phosphorescent materials [Tang, M.-C.; Chan, A. K.-W.; Chan, M.-Y.; Yam, V. W.-W. Top. Curr. Chem. 4, 374 (2016)]. The benchmark complex is the 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum (II) [Pt(OEP)] complex as a phosphorescent dopant for organic light-emitting devices (OLEDs), which was first demonstrated by Thompson and Forrest in 1998 [Baldo, M. A.; O'Brien, D. F.; You, A.; Shoustikov, A.; Sibley, S.; Thompson, M. E.; Forrest, S. R Nature 395, 151 (1998)]. Of particular interest are cyclometallated platinum (II) complexes. Constable and co-workers first reported the coordination of 6-phenyl-2,2'-bipyridine (phbpy) as a tridentate C^N^N ligand to a platinum(II) metal center [Constable, EC; Henney, RPG; Leese, TA; Tocher, DAJ Chem. Soc. Dalton. Trans. 443 (1990)]. Subsequently, the same group reported a series of related cyclometalated platinum(II) complexes [Pt(thbipy)X] (thbipy = 6-(2-thienyl)-2,2'-bipyridine and X = Cl, P(O)(OMe)2 or acetylacetone) with 6-(2-thienyl)-2,2'-bipyridine as a C^N^N tridentate ligand [Constable, EC; Henney, RPG; Raithby, PR; Sousa, LRJ Chem. Soc. Dalton. Trans. 2251 (1992)]. Che and co-workers further explored the luminescent properties of this system [Lai, S.-W.; Chan, M.C.-W.; Cheung, T.-C.; Peng, S.-M.; Che, C.-M. Inorg. Chem. 38, 4046 (1999)]. In addition to the tridentate C^N^N ligand, Cárdenas and co-workers demonstrated for the first time cyclometallated platinum (II) complexes of 1,3-dipyridylbenzene (N^C^N) [Cárdenas, DJ; Echavarren, AM; de Arellano, MCR Organometallics 18, 3337 (1999)]. Such complexes emit strongly in degassed dichloromethane at room temperature, achieving a high photoluminescence quantum yield (PLQY) of 68%.Recently, Yam and co-workers reported a new class of luminescent cyclometallated platinum (II) complexes with 2,6-bis (N-alkylbenzimidazol-2'-yl) benzene as N^C^N ligands and demonstrated strong green emission with a PLQY of 19% in dichloromethane solution and 45% in solid thin film [Tam, AY-Y.; Tsang, DP-K.; Chan, M.-Y.; Zhu, N.; Yam VW-W. Chem. Commun. 47, 3383 (2011)]. Multilayer phosphorescent OLEDs (PHOLEDs) based on this complex showed bright green electroluminescence (EL) with up to 38.9 cd A. -1 The high current efficiency (CE) and external quantum efficiency (EQE) of up to 11.5% [Tam, AY-Y.; Tang, DP-K.; Chan, M.-Y.; Zhu, N.; Yam VW-W. Chem. Commun. 47, 3383 (2011)]. Considering their unsaturated coordination properties with planar square structures and their huge synthetic diversity, various d-type ligands with monodentate, bidentate, tridentate and tetradentate ligands have been reported. 8 Platinum(II) complexes, where their emission energies span the entire visible spectrum from blue to red. Notably, through the coordination of the multidentate ligand to the platinum(II) metal center via a covalent metal-carbon bond, the strong σ-donating carbanion will make the 5d x 2 –y 2 The orbital is highly unstable, making the non-radiative dd ligand field excited state much more energetic. This in turn makes the non-radiative pathway less competitive than the emission pathway, thus enhancing the luminescence of the Pt(II) system.

[0005] Although platinum(II) complexes are known to display a wealth of luminescent properties, other isoelectronic 8 Transition metal complexes with transition metal centers are relatively poorly studied, especially due to their lack of luminescence at room temperature. The presence of thermally accessible and low-energy dd-ligand field excited states will quench the luminescent excited states through thermal equilibrium or energy transfer. However, the introduction of strong donor ligands to gold(III), i.e., d 8The coupling of strong σ-donating alkynyl or aryl ligands to gold(III) should make the metal center more electron-rich and have the added advantage of further raising the energy of the dd states, which will lead to enhanced luminescence by increasing the chances of filling the emissive state. Yam and co-workers built on their earlier strategy of introducing strong σ-donating aryl and alkyl ligands into gold(III) diimine complexes to obtain room temperature phosphorescent gold(III) complexes [Yam, VWW; Choi, SWK; Lai, TF; Lee, WKJ Chem. Soc., Dalton J. Chem. Soc., et al. Trans. 1001 (1993)], and the design and synthesis of a strongly luminescent cyclometallated acetylenic gold (III) complex [Au(R–C^N(R')^C–R)(C≡C–R)] (R–HC^N^CH=2,6-diphenylpyridine or substituted 2,6-diphenylpyridine; R=alkyl, aryl or substituted aryl; R'=aryl or substituted aryl) at room temperature were first demonstrated [Yam, VW-W.; Wong, KM-C.; Hung, L.-L.; Zhu, N. Angew.Chem.Int.Ed.44,3107(2005); Wong,KM-C.; Hung,L.-L.; Lam,WH; Zhu,N.; Yam,VW-WJ Am.Chem.Soc.129,4350(2007); Wong,KM-C.; Zhu,X.; Hung,L.-L.; Zhu,N.; Yam,VW-W.; Kwok,HS Chem.Commun.2906(2005)]. Recently, a new class of phosphorescent cyclometallated alkyne gold(III) complexes has been reported [Au,VK-M.; Wong,KM-C.; Tsang,DP-K.; Chan,MY; Yam,VW-WJ Am.Chem.Soc.132,14273(2010)]. Vacuum-deposited OLEDs achieve high EQE of 11.5% and 37.4 cd A -1CE. Later, dendritic gold (III) complexes have been designed and synthesized. The excellent solubility of these complexes in most organic solvents enables solution processing techniques to be used for OLED fabrication [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.; Yam, V.W. Chem. Eur. J. 20, 15233 (2014)]. Bipolar gold(III) complexes with N-phenylbenzimidazole as acceptor and triphenylamine as donor have also been developed [Tang, M.-C.; Tsang, D.P.-K.; Wong, Y.-C.; Chan, M.-Y.; Wong, K.M.-C.; Yam, V.W.-W. Am. Chem. Soc. 136, 17861 (2014)]. -2Based on this bipolar system, high EQE up to 10.0% and very small efficiency roll-off values ​​of less than 1% have been achieved at practical brightness levels. This design strategy can also be used to produce luminescent palladium (II) complexes. In 1997, Neve and his colleagues reported a new palladium (II) complex supported by a C^N^N ligand (C^N^N = 4'-[4-(dodecyloxy)phenyl]-6'-phenyl-2,2'-bipyridine) [Neve, F.; Crispini, A.; Campagna, S. Inorg. Chem. 36, 6150 (1997)]. This palladium (II) complex shows weak unstructured emission at 490nm. Recently, Che and co-workers reported a series of palladium (II) complexes [Pd (R-C^N^N-R')X] (R-C^N^N-R' = 3-(6'-aryl-2'-pyridyl) isoquinoline); X = chloride and pentafluorophenylacetylide) [Chow, P.-K.; To, W.-P.; Low, K.-H.; Che, C.-M. Chem. Asian. J. 9, 534 (2013)]. It was found that the cyclometallated palladium (II) complexes coordinated with chloride ion ligands only emitted at 77 K in the solid state and glassy solution. On the other hand, by incorporating pentafluorophenylacetylide ligands, the palladium (II) complexes showed strong phosphorescence in both the solid state and solution at room temperature. In addition, the luminescence properties of the metal complexes are closely related to the denticity of the chelating ligands. For planar square metal complexes, it seems that their thermal stability and rigidity are very important for device performance and lifetime. By using rigid tetradentate ligands to confine the metal center, higher stability and reduced non-radiative decay rates can be achieved. For example, the first tetradentate platinum (II) metal complex used as a light-emitting material was [Pt (OEP)] [Baldo, MA; O'Brien, DF; You, A.; Shoustikov, A.; Sibley, S.; Thompson, ME; Forrest, SR Nature 395, 151 (1998)]. Doped electroluminescent devices based on this emitter showed peak external and internal quantum efficiencies of 4% and 23%, respectively. Recently, it was reported that a rigid tetradentate O^N^C^N platinum (II) complex has a photoluminescence quantum yield of 90% and shows good thermal stability. Due to these advantages, PHOLEDs with high device efficiency and stability have been achieved, with an EQE of 18.2% and a current efficiency of 66.7 cd A –1[Kui, S. C. F.; Chow, P. K.; Cheng, G. C.; Kwok, C.-C.; Kwong, C. L.; Low, K.-H.; Che, C.-M. Chem. Comm. 49, 1497 (2013)]. In addition to platinum (II) complexes, Yam and co-workers also demonstrated the use of post-synthetic ligand modification methods to generate a new class of tetradentate gold (III) complexes that show ultrahigh photoluminescence quantum yields of up to 78% [Wong, B. Y.-W.; Wong, H.-L.; Wong, Y.-C.; Chan, M.-Y.; Yam, V. W.-W. Angew. Chem. Int. Ed. 55, 1 (2016)]. These complexes were found to catalyze photoinduced aerobic oxidation of amines for CH functionalization and photoinduced hydrogen production. It should be noted that the above-mentioned complexes are based on rare, expensive and noble transition metals, which limits their widespread use in commercial applications. Therefore, more affordable transition metal complexes with potential applications in commercial settings are being sought and remain an unmet need.

[0006] Isoelectronic d 8 The catalytic properties of nickel(II) complexes have been shown to be promising, and the complexes are generally low-cost alternatives to palladium and platinum-catalyzed cross-coupling reactions such as the Suzuki-Miyaura and Negishi reactions [Tasker, SZ; Standley, EA; Jamison, TF Nature 509, 299 (2014)]. However, isoelectronic d 8Nickel (II) complexes are non-emissive at room temperature and have been found to be only weakly emissive in the solid state or in glasses at low temperatures [Shields, BJ; Kudisch, B.; Scholes, GD; Doyle, AGA; Am. Chem. Soc. 140, 3035 (2018); Klein, A.; Rausch, B.; Kaiser, A.; Vogt, N.; Krest, AJ; Organomet. Chem. 774, 86 (2014)]. The following examples illustrate the use of nickel (II) complexes in catalysis. Nickel is more electropositive than palladium and platinum, which promotes oxidative coupling reactions and allows the use of cross-coupling electrophiles that are significantly less reactive under palladium catalysis, such as phenol derivatives [Li, B.-J.; Yu, D.-G.; Sun, C.-L.; Shi, Z.-J. Eur. Chem. J. 17, 1728 (2011); Mesganaw, T.; Garg, NKOlg. Process Res. Dev. 17, 29 (2013)], aromatic nitriles [Garcia, JJ; Brunkan, NM; Jones, WDJ Am. Chem. Soc. 124, 9547 (2002)] or aromatic fluorides [Tobisu, M.; Xu, T.; Shimasaki, T.; Chatani, NJ Am. Chem. Soc. 133, 19505 (2011)]. In 2003, Fu and co-workers reported the use of Ni(cod)2 (cod = 1,5-cyclooctadiene) in combination with a neutral tridentate bis(oxazoline) ligand to catalyze the Negishi cross-coupling of primary alkyl halides with alkylzinc reagents, representing the first nickel-catalyzed method for the cross-coupling of unactivated secondary alkyl halides containing β-hydrogen [Zhou, J.; Fu, GCG JAm. Chem. Soc. 125, 14726 (2003)]. In 2006, Morales and co-workers reported the design and synthesis of a tridentate nickel hypophosphite (II) complex [NiCl{C6H3-2,6-(OPPh2)2}] that catalyzes the thiolation of iodobenzenes with a wide range of disulfides in the presence of zinc [Gómez-Benítez, V.; Baldovino-Pantaleón, O.; Herrera- C.; Toscano, R. A.; Morales-Morales, D. Tetrahedron Lett. 47, 5059 (2006)]. Despite the interest in the use of nickel(II) complexes for catalysis, the chemistry of cyclometallated nickel(II)s is largely unexplored and underdeveloped, and their luminescent properties are virtually unknown. Notably, nickel (i.e., a row 1 transition metal) has the weakest dd splitting energy when compared to Group 10 analogs including palladium (row 2 transition metal) and platinum (row 3 transition metal). As a result, transition metal complexes with weak dd splitting energies comparable to those of nickel(II) complexes are non-emissive and are considered unsuitable when designing luminescent transition metal complexes. Therefore, there remains a need to develop improved and cost-effective transition metal complexes so that products containing OLEDs can have improved efficiency and be more affordable.

[0007] It was therefore an object of the present invention to provide improved luminescent transition metal complexes.

[0008] Another object of the present invention is to provide a luminescent transition metal complex containing a cyclometallated ligand having a dentate of three or more (eg, four) and an ancillary ligand.

[0009] Another object of the present invention is to provide a luminescent transition metal complex comprising a d- 6 ,d 7 or 8 transition metal centre, and ancillary ligands.

[0010] Another object of the present invention is to provide luminescent transition metal complexes comprising a nickel (II) center surrounded by a cyclometallated ligand having a dentate of three or more (eg, four) and an ancillary ligand. Summary of the invention

[0011] Transition metal complexes or compounds containing central metal atoms that are generally known to have weak dd splitting energies, such as those of nickel (II) complexes, are described herein. The cyclometallated ligands surrounding the central metal atom generally have a degree of denticity of three or more. However, the introduction of auxiliary ligands with strong σ-donating properties makes the metal center more electron-rich, with the added advantage of further increasing the energy of the dd state, which will lead to enhanced luminescence by increasing the chance of filling the emissive state. Preferably, the compounds are emissive in various media at room temperature and / or low temperatures, making them useful as light-emitting materials for OLEDs.

[0012] The luminescent compound has the following formula: in: M is a first row transition metal (e.g., scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc), preferably, M is nickel or copper; X, Y and Z are independently nitrogen or carbon; A, B and C are phenyl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted heterocyclic or substituted heterocyclic ring derivatives, wherein the dotted line represents R 1 Optionally connected to C or not, preferably, R 1 not connected to C; preferably, ring A, B and C are independently benzene, phenyl derivatives, unsubstituted heteroaryl, substituted heteroaryl, heteroaryl derivatives, unsubstituted heterocycle, substituted heterocycle or heterocycle derivatives (each optionally independently having one or more unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted aryl, unsubstituted cycloalkyl, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SOR, halogen, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl or unsubstituted heterocyclic groups, wherein R is independently unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted alkaryl, unsubstituted aryl or unsubstituted cycloalkyl); R 1 is any carbon or heteroatom donor ligand, halide or pseudohalide, which may be monoanionic or neutral. 1 is selected from, but not limited to, unsubstituted alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted alkynyl, substituted alkynyl, unsubstituted alkoxy, amide, thiolate, phosphide, chloride, bromide, iodide, cyanate, thiocyanate, cyanide, isocyanide, or N-heterocyclic carbene; and n is 0, a positive integer, or a negative integer. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 Shown are the UV-visible absorption spectra of Compounds 1, 2, 3 and 4 according to one or more embodiments herein in dichloromethane at 298K.

[0014] Figure 2 Shown are normalized photoluminescence spectra of Compounds 1 and 3 according to one or more embodiments herein in dichloromethane at 298 K.

[0015] Figure 3 Shown is the normalized photoluminescence spectrum of Compound 2 according to one or more embodiments herein in degassed toluene at 298 K.

[0016] Figure 4 The normalized photoluminescence spectrum of compound 2 in the solid state at 77 K is shown.

[0017] Figure 5 The normalized photoluminescence spectrum of compound 2 in the solid state at 298 K is shown.

[0018] Figure 6 Normalized photoluminescence spectra of thin films of 10 wt % of Compound 2 doped into 1,3-bis(carbazol-9-yl)benzene (MCP) at 298 K are shown.

[0019] Figure 7 EL spectra of a solution-processable OLED having Compound 2 doped into MCP as the light-emitting layer according to one or more embodiments herein are shown. Inset: A magnified view of the EL spectrum showing the emission band of Compound 2.

[0020] Figure 8 Schematic diagram of a light emitting device. The device comprises (i) a cathode 110 including a first layer 120 and a second layer 130; (ii) an electron transport layer 140; (iii) a carrier confinement layer 150; (iv) a light emitting layer 160; (v) a hole transport layer 170; and (vi) an anode 180. DETAILED DESCRIPTION OF THE INVENTION I. Definitions The term "room temperature" refers to a temperature of about 288K to about 303K, for example 308K.

[0022] The term "low temperature" refers to a temperature of about 70K to about 150K, for example 77K.

[0023] The term "cyclometallated ligand" includes, but is not limited to, 1,3-bis(2-pyridyl)benzene (N^C^N), 1,3-di(pyridin-2-yl)-5-tert-butylbenzene (N^C t Bu^N), 1,3-di(isoquinolyl)-5-tert-butylbenzene (N (isoquin) ^C t Bu^N (isoquin) ), 1,3-di(pyridin-2-yl)-5-phenylbenzene (N^CPh^N), 1,3-difluoro-4,6-di(pyridin-2-yl)benzene (N^C6H2F2^N), 1,3-difluoro-4,6-di(4-tert-butylpyridin-2-yl)benzene (N^C6H2F2^N), 1,3-di(pyridin-2-yl)-5-(4-isopropylphenyl)benzene (N^C(4- iPr-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(4-nitrophenyl)benzene (N^C(4-NO2-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(4-methoxyphenyl)benzene (Ph–N^C(4-OMe-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(4-methylphenyl)benzene (N^C(4-Me-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(4-ethylphenyl)benzene (N^C(4-C2H5-C 6H4)^N), 1,3-di(pyridin-2-yl)-5-(2,3,4-trimethoxyphenyl)benzene (N^C(2,3,4-OMe-C6H2)^N), 1,3-di(pyridin-2-yl)-5-(4-toluenesulfonylphenyl)benzene (N^C(4-OTs-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(4-dimethylaminophenyl)benzene (N^C(4-NMe2-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(4-diphenylaminophenyl)benzene ( N^C(4-NPh2-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(4-bromophenyl)benzene (N^C(4-Br-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(4-chlorophenyl)benzene (N^C(4-Cl-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(4-fluorophenyl)benzene (N^C(4-F-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(4-iodophenyl)benzene (N^C(4-I-C6H4)^N ), 1,3-di(pyridin-2-yl)-5-(2,5-dimethylphenyl)benzene (N^C(2,5-Me2-C6H4)^N), 1,3-di(pyridin-2-yl)-5-(2,3,4,5,6-pentafluorophenyl)benzene (N^C(C6F5)^N), 2-(9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C^N^O), 2-(7-(tert-butyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C t Bu^N^O), 2-(3-(isoquinolin-3-yl)-11,12-dihydrobenzo[c]phenanthridin-6-yl)phenol (N (isoquin) ^C^N (isoquin) ^O), 2-(7-phenyl-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^CPh^N^O), 2-(7-(4-isopropylphenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(4- iPr-C6H4)^N^O), 2-(7-(4-nitrophenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(4-NO2–C6H4)^N^O), 2-(7-(4-methoxyphenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(4-OMe-C6H4)^N^O), 2-(9-(pyridin-2-yl)-7-(p-tolyl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol 2-(7-(4-(dimethylamino)phenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(4-NMe2-C6H4)^N^O), 2-(7-(4-(dimethylamino)phenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(4-NMe2-C6H4)^N^O), 2-(7-(4-(diphenylphosphane)-1-nitropropene)-1-nitropropene)-1-nitropropene)-1-nitropropene)-1-nitropropene)-1-nitropropene)-1-nitropropene)-1-nitropropene)-1-nitropropene)-1-nitropropene 2-(7-(4-bromophenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(4-NPh2-C6H4)^N^O), 2-(7-(4-bromophenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(4-Br-C6H4)^N^O), 2-(7-(4-chlorophenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(4-Cl-C6H4)^N^O ), 2-(7-(4-fluorophenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(4-F-C6H4)^N^O), 2-(7-(4-iodophenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(4-I-C6H4)^N^O), 2-(7-(perfluorophenyl)-9-(pyridin-2-yl)-5,6-dihydrobenzo[h]quinolin-2-yl)phenol (N^C(C6F5)^N^O).

[0024] "Pseudohalide" includes, but is not limited to, cyanate, thiocyanate, and cyanide.

[0025] "Alkyl" includes straight and branched alkyls, and cycloalkyls in which the alkyl has a ring structure. Preferred alkyls are those containing 1 to 18 carbon atoms, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and other similar compounds. In addition, the alkyl may be optionally substituted with one or more substituents selected from hydrogen atoms, deuterium atoms, formaldehyde, cyano, alkyl alkynyl, substituted alkyl alkynyl, aryl alkynyl, substituted aryl alkynyl, heteroaryl alkynyl, substituted heteroaryl alkynyl, fused polycyclic, substituted fused polycyclic, aryl, alkyl, heteroaryl, nitro, trifluoromethane, cyano, aryl ether, alkyl ether, heteroaryl ether, diarylamine, dialkylamine, diheteroarylamine, diarylborane, triarylsilane Alkyl, trialkylsilane, alkenyl, alkylaryl, cycloalkyl, haloformyl, hydroxyl, aldehyde, carboxamide, amine, amino, alkoxy, azo, benzyl, carbonate, carboxylate, carboxyl, ketamine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phosphate, phosphono, pyridyl, sulfonyl, sulfo, sulfinyl, mercapto, halogen, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle and derivatives thereof.

[0026] Those skilled in the art will appreciate that, if appropriate, the substituent moiety on the hydrocarbon chain itself may be substituted. For example, the substituent of the substituted alkyl may include halogen, hydroxyl, nitro, sulfhydryl, amino, azido, imino, amide, phosphoryl (including phosphonates and phosphinates), sulfonyl (including sulfates, sulfonamido, sulfamoyl and sulfonates) and silyl, as well as ethers, alkylthio, carbonyl (including ketones, aldehydes, carboxylates and esters), haloalkyl, -CN, etc. Cycloalkyl may be substituted in the same manner.

[0027] As used herein, "substituted" refers to all permissible substituents of the compounds or functional groups described herein. In the broadest sense, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. Exemplary substituents include, but are not limited to, halogen, hydroxyl, or any other linear, branched or cyclic organic group containing any number of carbon atoms (preferably, 1-14 carbon atoms) and optionally including one or more heteroatoms such as oxygen, sulfur, or nitrogen. Representative substituents include alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, phenyl, substituted phenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, halogen, hydroxy, alkoxy, substituted alkoxy, phenoxy, substituted phenoxy, aryloxy, substituted aryloxy, alkylthio, substituted alkylthio, phenylthio, substituted phenylthio, arylthio, substituted arylthio, cyano, isocyano, substituted isocyano, carbonyl, substituted carbonyl, carboxyl, substituted carboxyl, amino, substituted amino, amido, substituted amido, sulfonyl, substituted sulfonyl, sulfonic acid, phosphoryl, substituted phosphoryl, phosphonyl, substituted phosphonyl, polyaryl, substituted polyaryl, cyclic (e.g., C3-C4) 20 Cyclic), substituted cyclic (e.g. substituted C3-C 20cyclic), heterocyclic, substituted heterocyclic, amino acids, poly(lactic-co-glycolic acid), peptides, polypeptides, deuterium, unsubstituted alkyl alkynyl, substituted alkyl alkynyl, unsubstituted aryl alkynyl, substituted aryl alkynyl, unsubstituted heteroaryl alkynyl, substituted heteroaryl alkynyl, trihaloalkyl (trifluoromethyl), unsubstituted heteroaryl ether, substituted heteroaryl ether, unsubstituted diarylamino, substituted diarylamino, unsubstituted dialkylamino, substituted dialkyl amino, unsubstituted diheteroarylamino, substituted diheteroarylamino, unsubstituted diarylboryl, substituted diarylboryl, unsubstituted triarylsilyl, substituted triarylsilyl, unsubstituted trialkylsilyl, substituted trialkylsilyl, azo, carbonate, ketamine, nitro, nitroso, phosphino, pyridyl, NRR', SR, C(O)R, COOR, C(O)NR, SOR, SOR, and BR R' group, wherein R and R' are independently selected from hydrogen atoms, deuterium atoms, formaldehyde, cyano groups, alkyl alkynyl groups, substituted alkyl alkynyl groups, aryl alkynyl groups, substituted aryl alkynyl groups, heteroaryl alkynyl groups, substituted heteroaryl alkynyl groups, condensed polycyclic rings, substituted condensed polycyclic rings, aryl groups, alkyl groups, heteroaryl groups, nitro groups, trifluoromethane, cyano groups, aryl ethers, alkyl ethers, heteroaryl ethers, diarylamines, dialkylamines, diheteroarylamines, diarylboranes, triarylsilanes, trialkyl Silane, alkenyl, alkylaryl, cycloalkyl, haloformyl, hydroxy, aldehyde, carboxamide, amine, amino, alkoxy, azo, benzyl, carbonate, carboxylate, carboxyl, ketamine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phosphate, phosphono, pyridyl, sulfonyl, sulfo, sulfinyl, mercapto, halogen, aryl, substituted aryl, heteroaryl, substituted heteroaryl and heterocyclic groups. Such alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, phenyl, substituted phenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, halogen, hydroxy, alkoxy, substituted alkoxy, phenoxy, substituted phenoxy, aryloxy, substituted aryloxy, alkylthio, substituted alkylthio, phenylthio, substituted phenylthio, arylthio, substituted arylthio, cyano, isocyano, substituted isocyano, carbonyl, substituted carbonyl, carboxyl, substituted carboxyl, amino, substituted amino, amide, substituted amide, sulfonyl, substituted sulfonyl, sulfonic acid, phosphoryl, substituted phosphoryl, phosphonyl, substituted phosphonyl, polyaryl, substituted polyaryl, cyclic (e.g., C3-C 20 Cyclic), substituted cyclic (e.g. substituted C3-C 20The compounds may be substituted with any of the following: alkyl, aryl, arylalkyl, substituted arylalkyl, substituted arylalkyl, unsubstituted heteroarylalkynyl, substituted heteroarylalkynyl, trihaloalkyl (trifluoromethyl), unsubstituted heteroarylether, substituted heteroarylether, unsubstituted diarylamino, substituted diarylamino, unsubstituted dialkylamino, substituted dialkylamino, unsubstituted diheteroarylamino, substituted diheteroarylamino, unsubstituted diarylboranyl, substituted diarylboranyl, unsubstituted triarylsilyl, substituted triarylsilyl, unsubstituted trialkylsilyl, substituted trialkylsilyl, azo, carbonate, ketamine, nitro, nitroso, phosphide, phosphino and pyridinyl groups may be further substituted.

[0028] As used herein, the term "unsubstituted alkenylaryl group" includes an aryl group having an alkenyl group as a substituent.

[0029] The term "substituted alkenylaryl" refers to alkenylaryl groups having one or more substituents replacing one or more hydrogen atoms in the group.

[0030] As used herein, the term "unsubstituted alkynylaryl" includes an aryl group having an alkynyl group as a substituent.

[0031] The term "substituted alkynylaryl" refers to alkynylaryl groups having one or more substituents replacing one or more hydrogen atoms in the group.

[0032] As used herein, the term "unsubstituted alkylalkenyl" includes an alkenyl group having an alkyl group as a substituent.

[0033] The term "substituted alkylalkenyl" refers to alkylalkenyl groups having one or more substituents replacing one or more hydrogen atoms in the group.

[0034] As used herein, the term "unsubstituted arylalkenyl" includes an alkenyl group having an aryl group as a substituent.

[0035] The term "substituted arylalkenyl" refers to arylalkenyl groups having one or more substituents replacing one or more hydrogen atoms in the group.

[0036] The term "substituted alkynylalkenyl" refers to alkynylalkenyl groups having one or more substituents replacing one or more hydrogen atoms in the group.

[0037] As used herein, the term "unsubstituted alkynylalkenyl" includes an alkenyl group having an alkynyl group as a substituent.

[0038] As used herein, the term "unsubstituted alkylalkynyl" includes an alkynyl group having an alkyl group as a substituent.

[0039] The term "substituted alkylalkynyl" refers to alkylalkynyl groups having one or more substituents replacing one or more hydrogen atoms in the group.

[0040] As used herein, the term "unsubstituted arylalkynyl" includes an alkynyl group having an aryl group as a substituent.

[0041] The term "substituted arylalkynyl" refers to arylalkynyl groups having one or more substituents replacing one or more hydrogen atoms in the group.

[0042] As used herein, the term "heteroatom" includes, but is not limited to, S, O, N, P, Se, Te, As, Sb, Bi, B, Si, Ge, Sn, and Pb. Heteroatoms such as nitrogen may have hydrogen substituents and / or any permissible substituents of the organic compounds described herein that satisfy the valences of the heteroatoms. It should be understood that "substitution" or "substituted" includes the implicit condition that such substitution is in accordance with the permissible valences of the substituted atom and the substituent, and that the substitution produces a stable compound, i.e., a compound that does not spontaneously undergo transformation, such as by rearrangement, cyclization, elimination, etc.

[0043] As used herein, the term "alkenyl" is a hydrocarbon group having, for example, 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (AB)C=C(CD) are intended to include E and Z isomers. This can be inferred from the structural formulas in which asymmetric olefins are present herein, or can be explicitly indicated with the bond symbol C.

[0044] As used herein, the term "alkynyl" is a hydrocarbon group having, for example, 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond.

[0045] As used herein, the term "aryl" is any C5-C 26 As used herein, "aryl" is broadly defined to include 5-, 6-, 7-, 8-, 9-, 10-, 14-, 18- and 24-membered monocyclic aromatic groups, including but not limited to benzene, naphthalene, anthracene, phenanthrene, , pyrene, corannulene, coronene, etc. "Aryl" also includes a polycyclic ring system with two or more cyclic rings, wherein two or more carbons are shared by two adjacent rings (i.e., "condensed rings"), wherein at least one ring is aromatic, for example, the other one or more cyclic rings may be cycloalkyl, cycloalkenyl, cycloalkynyl, aryl and / or heterocycle. The aryl may be substituted by one or more groups, including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halogen, nitro, amino, ester, ketone, aldehyde, hydroxyl, carboxylic acid or alkoxy.

[0046] The term "substituted aryl" refers to an aryl group in which one or more hydrogen atoms on one or more aromatic rings are replaced by one or more substituents, including but not limited to halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxy, alkoxy, carbonyl (e.g., ketone, aldehyde, carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, imino, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl (e.g., CF3, -CH2-CF3, -CCl3), -CN, aryl, heteroaryl, and combinations thereof.

[0047] "Heterocycle", "heterocyclic" and "heterocyclyl" are used interchangeably and refer to a cyclic group attached through a monocyclic or bicyclic ring carbon or nitrogen atom, containing 3-10 ring atoms, preferably 5-6 ring atoms, consisting of carbon and one to four heteroatoms, each heteroatom selected from non-peroxidized oxygen, sulfur and N(Y), wherein Y is absent or is H, O, C1-C 10 Alkyl, phenyl or benzyl, and optionally containing 1-3 double bonds and optionally substituted by one or more substituents. The definition of heterocyclic radical is different from that of heteroaryl. Examples of heterocycles include, but are not limited to, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, dihydrofuran [2,3-b] tetrahydrofuran, morpholinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pyranyl, 2H-pyrrolyl, 4H-quinolizinyl, quinuclidinyl, tetrahydrofuranyl, 6H-1,2,5-thiadiazinyl. Heterocyclic radicals may be optionally substituted by one or more substituents as defined above for alkyl and aryl.

[0048] The term "heteroaryl" refers to a C5-C 26The term "heteroaryl" refers to a 5-, 6-, 7-, 8-, 9-, 10-, 14-, 18- and 24-membered monocyclic aromatic group, which may include one to four heteroatoms, such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, tetrazole, pyrazole, pyridine, pyrazine, pyridazine and pyrimidine. Heteroaryl may also be referred to as "aryl heterocycle" or "heteroaromatic compound". "Heteroaryl" also includes a polycyclic ring system with two or more rings, wherein two or more carbon atoms are shared by two adjacent rings (i.e., "fused ring"), wherein at least one ring is heteroaromatic, for example, other one or more rings may be cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocycle or a combination thereof. Examples of heteroaryl rings include, but are not limited to, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzothiazolyl, benzotriazolyl, benzotetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl, chromenyl, cinnolinyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, dihydroindolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, naphthyridinyl, octahydroisoquinolinyl, 1,2,3-oxadiazolyl, oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxathiyl, phenoxazinyl, phthalazinyl, pteridinyl, purinyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole, pyridinyl ... ), pyridyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, quinazolinyl, quinolyl, quinoxalinyl, tetrahydroisoquinolyl, tetrahydroquinolyl, tetrazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thienyl, and xanthenyl. One or more rings may be substituted as defined below for "substituted heteroaryl".

[0049] The term "substituted heteroaryl" refers to a heteroaryl group in which one or more hydrogen atoms on one or more heteroaryl rings are replaced with one or more substituents, including but not limited to halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxy, alkoxy, carbonyl (e.g., ketone, aldehyde, carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, imine, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl (e.g., CF3, -CH2-CF3, -CCl3), -CN, aryl, heteroaryl, and combinations thereof.

[0050] The term "substituted alkenyl" refers to an alkenyl moiety having one or more substituents that replace one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone. Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0051] The term "substituted alkynyl" refers to an alkynyl moiety having one or more substituents that replace one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone. Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0052] As used herein, the term "cycloalkyl" is a non-aromatic carbon-based ring consisting of at least three carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term "heterocycloalkyl" is a cycloalkyl as defined above, wherein at least one carbon atom of the ring is replaced by a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.

[0053] As used herein, the term "aralkyl" is an aryl group having an alkyl, alkynyl or alkenyl group as defined above attached to the aryl group. An example of an aralkyl group is benzyl.

[0054] As used herein, the term "hydroxyalkyl" is an alkyl, alkenyl, alkynyl, aryl, aromatic hydrocarbon group, cycloalkyl, halogenated alkyl or heterocycloalkyl group as described above, in which at least one hydrogen atom is replaced by a hydroxy group.

[0055] The term "alkoxyalkyl" is defined as the above-mentioned alkyl, alkenyl, alkynyl, aryl, aromatic hydrocarbon group, cycloalkyl, halogenated alkyl or heterocycloalkyl group, at least one hydrogen atom of which is replaced by the above-mentioned alkoxy group.

[0056] As used herein, "carbonyl" is art-recognized and includes moieties such as those represented by the following general formula: wherein X is a bond, or represents oxygen or sulfur, and R represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, -(CH2) m -R" or a pharmaceutically acceptable salt thereof, R' represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl or -(CH2) m -R"; R" represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle or a polycycle; and m is 0 or an integer from 1 to 8. When X is oxygen and R is as defined above, the moiety is also referred to as a carboxyl group. When X is oxygen and R is hydrogen, the formula represents a "carboxylic acid". When X is oxygen and R' is hydrogen, the formula represents a "formatic ester". When X is oxygen and R or R' is not hydrogen, the formula represents an "ester". Generally, when the oxygen atom of the above formula is replaced by a sulfur atom, the formula represents a "thiocarbonyl". When X is sulfur and R or R' is not hydrogen, the formula represents a "thioester". When X is sulfur and R is hydrogen, the formula represents a "thiocarboxylic acid". When X is sulfur and R' is hydrogen, the formula represents a "thioformate". When X is a bond and R is not hydrogen, the above formula represents a "ketone". When X is a bond and R is hydrogen, the above formula represents an "aldehyde".

[0057] The term "substituted carbonyl" refers to a carbonyl group as defined above, wherein one or more hydrogen atoms in R, R' or the group to which the following moieties are attached are independently substituted:

[0058] Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0059] The term "carboxyl" is as defined above for the formula And more specifically by the formula -R iv COOH definition, where R iv The alkyl radicals are alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkylaryl, arylalkyl, aryl or heteroaryl. In preferred forms, the straight or branched chain alkyl, alkenyl and alkynyl radicals have 30 or fewer carbon atoms in their backbone (e.g., C1-C2 of a straight chain alkyl radical). 30 , branched alkyl C3-C 30 , straight chain alkenyl and alkynyl C2-C 30 , branched alkenyl and alkynyl C3-C 30 ), preferably 20 or less, more preferably 15 or less, most preferably 10 or less. Likewise, preferred cycloalkyl, heterocyclyl, aryl and heteroaryl groups have 3-10 carbon atoms in their ring structure, and more preferably have 5, 6 or 7 carbons in the ring structure.

[0060] The term "substituted carboxyl" refers to a carboxyl group as defined above, wherein R iv One or more hydrogen atoms in are replaced. Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0061] The term "phenoxy" is recognized and refers to a radical of the formula -OR v A compound wherein R vThose skilled in the art will recognize that phenoxy is one of the aryloxy groups.

[0062] The term "substituted phenoxy" refers to a phenoxy group as defined above having one or more substituents replacing one or more hydrogen atoms on one or more carbons of a benzene ring. Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl and combinations thereof.

[0063] The terms "aryloxy" and "aryloxy" used interchangeably herein are represented by -O-aryl or -O-heteroaryl, wherein aryl and heteroaryl are as defined herein.

[0064] The terms "substituted aryloxy" and "substituted aryloxy" used interchangeably herein refer to -O-aryl or -O-heteroaryl groups having one or more substituents replacing one or more hydrogen atoms on one or more ring atoms of aryl and heteroaryl groups as defined herein. Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0065] The term "alkylthio" refers to an alkyl group as defined above having a sulfenyl group attached thereto. The "alkylthio" portion is represented by -S-alkyl. Representative alkylthio groups include methylthio, ethylthio, and the like. The term "alkylthio" also includes a cycloalkyl group having a sulfenyl group attached thereto.

[0066] The term "substituted alkylthio" refers to an alkylthio having one or more substituents that replace one or more hydrogen atoms on one or more carbon atoms of the alkylthio skeleton. Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0067] The term "phenylthio" is art-recognized and refers to -S-C6H5, a phenyl group attached to a sulfur atom.

[0068] The term "substituted phenylthio" refers to a phenylthio group as defined above having one or more substituents replacing hydrogen on one or more carbons of the phenyl ring. Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl and combinations thereof.

[0069] "Arylthio" means an -S-aryl or -S-heteroaryl group wherein aryl and heteroaryl are as defined herein.

[0070] The term "substituted arylthio" means -S-aryl or -S-heteroaryl having one or more substituents replacing hydrogen atoms on one or more ring atoms of aryl and heteroaryl rings as defined herein. Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, -CN, aryl, heteroaryl and combinations thereof.

[0071] The terms "amide" or "amido" are used interchangeably to refer to both "unsubstituted amide" and "substituted amide" and are represented by the following general formula: wherein E is absent or E is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aromatic hydrocarbon, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocyclyl, wherein R and R' independently of E each independently represent hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, -(CH2) m -R"', or R and R' together with the N atom to which they are attached form a heterocycle having 3 to 14 atoms in the ring structure; R"' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle or a polycycle; and m is 0 or an integer from 1 to 8. In a preferred form, only one of R and R' can be a carbonyl group, for example, R and R' do not form an imide together with nitrogen. In a preferred form, R and R' each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or -(CH2) m -R"'. When E is oxygen, a carbamate is formed. The carbamate cannot be linked to other chemical species, for example to form an oxygen-oxygen bond or other unstable bonds, as understood by those of ordinary skill in the art.

[0072] The term "sulfonyl" is represented by the formula wherein E is absent or E is alkyl, alkenyl, alkynyl, arene, alkylaryl, cycloalkyl, aryl, heteroaryl, heterocyclyl, wherein R, independently of E, represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted amine, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, -(CH2) m -R"', or E and R together with the S atom to which they are attached form a heterocycle having 3 to 14 atoms in the ring structure; R"' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle or a polycycle; and m is 0 or an integer from 1 to 8. In a preferred form, only one of E and R can be a substituted or unsubstituted amine to form a "sulfonamide" or "sulfonamido". The substituted or unsubstituted amine is as defined above.

[0073] The term "substituted sulfonyl" refers to a sulfonyl group in which E, R or both are independently substituted. Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0074] The term "sulfonic acid" refers to a sulfonyl group as defined above, wherein R is hydroxy and E is absent, or E is substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl.

[0075] The term "sulfate" refers to a sulfonyl group as defined above, wherein E is absent, oxygen, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy (as defined above), and R is independently hydroxy, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy (as defined above). When E is oxygen, sulfate cannot be attached to other chemical species, for example to form an oxygen-oxygen bond, or other unstable bonds, as understood by those of ordinary skill in the art.

[0076] The term "sulfonate" refers to a sulfonyl group as defined above, wherein E is oxygen, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy (as defined above), and R is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted amine, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, -(CH2) m -R"', R"' represents hydroxyl, substituted or unsubstituted carbonyl, aryl, cycloalkyl ring, cycloalkenyl ring, heterocycle or polycycle; and m is 0 or an integer from 1 to 8. When E is oxygen, the sulfonate cannot be attached to other chemical species, for example to form an oxygen-oxygen bond, or other unstable bonds, as understood by those of ordinary skill in the art.

[0077] The term "sulfamoyl" refers to a sulfonamide or sulfonamide group represented by the formula wherein E is absent or E is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aromatic hydrocarbon, substituted or unsubstituted alkylaryl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclyl, wherein R and R' independently of E each independently represent hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, -(CH2) m -R"', or R and R' together with the N atom to which they are attached form a heterocycle having 3-14 atoms in the ring structure; R"' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle or a polycycle; and m is 0 or an integer from 1 to 8. In a preferred form, only one of R and R' can be a carbonyl group, for example, R and R' do not form an imide together with nitrogen.

[0078] The term "phosphono" is represented by the formula wherein E is absent, or E is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aromatic hydrocarbon, substituted or unsubstituted alkylaryl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclyl, wherein, independently of E, R vi and R vii are independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, -(CH2) m -R"', or R and R' together with the P atom to which they are attached form a heterocyclic ring having 3-14 atoms in the ring structure; R"' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocyclic ring or a polycyclic ring; and m is 0 or an integer from 1 to 8.

[0079] The term "substituted phosphono" refers to a phosphono group in which E, R vi and R viiIndependently substituted phosphonyl groups. Such substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphite, amino (or quaternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0080] The term "phosphoryl" is defined as a phosphonyl group wherein E is absent, oxygen, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy (as defined above), and independently of E, R vi and R vii R is independently hydroxy, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy (as defined above). When E is oxygen, the phosphoryl group cannot be attached to other chemical species, for example to form an oxygen-oxygen bond, or other unstable bonds, as understood by those of ordinary skill in the art. vi and R vii When substituted, the substituents include, but are not limited to, halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0081] The term "polyaryl" refers to a chemical moiety comprising two or more aryl, heteroaryl, and combinations thereof. The aryl, heteroaryl, and combinations thereof are fused or connected by single bonds, ethers, esters, carbonyls, amides, sulfonyls, sulfonamides, alkyls, azos, and combinations thereof. When two or more heteroaryl groups are involved, the chemical moiety may be referred to as a "polyheteroaryl".

[0082] The term "substituted polyaryl" refers to a polyaryl in which one or more aryl, heteroaryl groups are substituted with one or more substituents, including but not limited to halogen, azide, alkyl, arene, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, -CN, aryl, heteroaryl and combinations thereof. When two or more heteroaryl groups are involved, the chemical moiety may be referred to as a "substituted polyheteroaryl".

[0083] The term "cyclic" refers to substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted cycloalkynyl, substituted or unsubstituted heterocyclic radical, preferably having 3 to 20 carbon atoms, as allowed by geometrical restrictions. The ring structure is formed by a monocyclic or condensed ring system. Substituted cycloalkyl, cycloalkenyl, cycloalkynyl and heterocyclic radical are substituted as defined above for alkyl, alkenyl, alkynyl and heterocyclic radical, respectively.

[0084] "Derivatives" related to a given compound or part refer to another compound or part that is structurally similar, functionally similar, or both similar to a specified compound or part. Any standard known in the art can be used to determine structural similarity, such as the Tanimoto coefficient, which provides a quantitative measure of the similarity between two compounds based on the molecular descriptors of the two compounds. Preferably, the molecular descriptor is a 2D property, such as a fingerprint, a topological index, and a maximum common substructure, or a 3D property, such as an overall shape and a molecular field. For dissimilar and identical molecular pairs, the range of the Tanimoto coefficient is 0 to 1, including 0 and 1. If the Tanimoto coefficient of a compound and a specified compound is 0.5 to 1.0, including 0.5 and 1.0, preferably 0.7 to 1.0, including 0.7 and 1.0, most preferably 0.85 to 1.0, including 0.85 and 1.0, then the compound can be regarded as a derivative of the specified compound. If the compound causes the same effect as the specified compound, the compound is functionally similar to the specified compound. "Derivatives" can also refer to modifications, including but not limited to hydrolysis, reduction or oxidation products of a compound or part. Hydrolysis, reduction and oxidation reactions are known in the art.

[0085] II. Composition This paper describes transition metal complexes containing central metal atoms that are generally known to have weak dd splitting energies. To the best of our knowledge, this work is the first demonstration of the use of luminescent nickel(II) complexes for the fabrication of OLEDs. Typically, planar square d 8 Metal complexes can be prepared by incorporating tridentate or tetradentate ligands into the 8 Preferably, the ligand is a cyclometalating ligand, ie, capable of forming a metal-carbon σ-bond.

[0086] It is generally believed that the thermally accessible and low-energy dd ligand field excited states present in these complexes quench the luminescence of the excited states through thermal equilibrium or energy transfer. However, the introduction of auxiliary ligands with σ-donating properties effectively enhances the luminescence of these complexes. The coupling of σ-donating ligands makes the metal center more electron-rich, with the additional advantage of further improving the energy of the dd state, which will lead to enhanced luminescence by increasing the chance of filling the emission state. Unlike most other planar square nickel (II) complexes that do not emit at low temperatures and ambient temperatures or only show luminescence at low temperatures, the complexes described herein are preferably photostable and emit light at room temperature, low temperatures, or a combination thereof in various media such as solid, liquid, or solution states. Therefore, transition metal complexes represent compounds that can be used as luminescent materials for OLEDs.

[0087] The present invention contemplates a variety of ligand structures and methods of use and preparation thereof. In certain embodiments, the ligand forms coordination complexes with various metal ions, particularly nickel (II).

[0088] A. Compounds Disclosed are luminescent organometallic complexes or compounds. In some forms, the luminescent compound has the formula: in: The compound has an overall negative charge, is neutral, or has a positive charge; M is a first row transition metal atom (e.g., scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc), preferably, M is nickel, copper, iron or cobalt, most preferably, M is nickel; M has an oxidation state of 0 to +7, inclusive, preferably an oxidation state of 0, +1, +2 or +3; A, B and C are each independently unsubstituted heteroaryl, substituted heteroaryl, unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, substituted C3-C 20 Cycloalkyl, unsubstituted C3-C 20 Cycloalkyl, substituted C3-C 20 Heterocyclic, unsubstituted C3-C20 Heterocyclic, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloalkynyl or unsubstituted C3-C 20 Cycloalkynyl, preferably, at least one of A, B and C is substituted aryl or unsubstituted aryl, and the other of A, B and C is substituted heteroaryl or unsubstituted heteroaryl, preferably, the bond between at least one of A, B and C and M is a metal-carbon σ-bond; wherein the dotted line represents R 1 Optionally connected to C or not, preferably, R 1 Not connected to C; q is 1 or 2, preferably 1; p is 1 (tridentate ligand), 2 (tetradentate ligand) or 3 (pentadentate ligand), preferably 1 and 2; G and J are each independently a bond (single bond, double bond, triple bond), absent, oxygen, sulfur, unsubstituted amino, substituted amino, unsubstituted alkylene, substituted alkylene, unsubstituted alkyl, substituted alkyl, substituted carbonyl, unsubstituted carbonyl, substituted carboxyl, unsubstituted carboxyl, substituted amide, unsubstituted amide, substituted sulfonyl, unsubstituted sulfonyl, substituted sulfonic acid, unsubstituted sulfonic acid, substituted phosphoryl, unsubstituted phosphoryl, substituted phosphonyl or unsubstituted phosphonyl; preferably, G and J are each a single bond; R 1 is a carbon or heteroatom donor ligand, a halide or pseudohalide, which may be monoanionic or neutral, such as unsubstituted heteroaryl (carbazole), substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, substituted aryl (4-tert-butylphenyl), unsubstituted aryl (phenyl), substituted C3-C 20 Heterocyclic group (substituted C3 heterocyclic group such as 1,3-dimethyl-2,3-dihydro-1H-imidazol-2-yl), unsubstituted C3-C 20Heterocyclic group (1,3-dimethyl-2,3-dihydro-1H-imidazol-2-yl), substituted N-alkylidene arylamine (2,6-dimethyl-N-ethylidene benzylamine), unsubstituted N-alkylidene arylamine (2,6-dimethyl-N-ethylidene benzylamine), unsubstituted arylalkynyl (phenylethynyl), substituted arylalkynyl (4-tert-butylphenylethynyl), unsubstituted alkyl, substituted alkyl, unsubstituted alkynyl, substituted Alkynyl, unsubstituted alkenyl (vinyl), substituted alkenyl (3,3-dimethylbutenyl, 2-phenylvinyl), unsubstituted aryl alkenyl (2-phenylvinyl), substituted aryl alkenyl (2-(3,5-di-tert-butylphenyl) vinyl), unsubstituted heteroaryl (pyridin-4-yl), substituted heteroaryl (2,6-dimethylpyridin-4-yl), halogen (chlorine, fluorine, bromine, iodine), cyano, substituted cyano, cyanate, isocyanate , isothiocyanate, thiocyanate, substituted amino (N,N-diarylamine such as N,N-diphenylamine), unsubstituted amino, phosphide, substituted phosphino (diarylphosphino such as diphenylphosphino), unsubstituted phosphino, hydroxy, unsubstituted alkoxy, substituted alkoxy, unsubstituted amide, substituted amide, unsubstituted aryloxy (phenoxy), substituted aryloxy, unsubstituted arylthio (phenylthio), substituted arylthio, unsubstituted substituted aryl seleno groups, unsubstituted aryl silyl groups (triaryl silyl groups such as triphenylsilyl groups), substituted aryl silyl groups, unsubstituted aryl boryl groups (diaryl boryl groups such as diphenyl boryl groups), substituted aryl boryl groups, unsubstituted alkyl boryl groups, substituted alkyl boryl groups, unsubstituted boryl groups, substituted boryl groups, sulfonate groups (trifluoromethanesulfonate groups) or N-heterocyclic carbene groups; r is 0, 1 or 2, preferably, r is 1; and optionally, wherein substituted refers to substitution by one or more substituents selected from unsubstituted alkyl, alkyl (tert-butyl) having one or more alkyl substituents, alkyl (trifluoromethyl) having one or more halogen substituents, halogen (chlorine, fluorine, bromine, iodine), unsubstituted aryl (phenyl), aryl (2,6-dimethylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl) having one or more alkyl substituents, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, substituted C3-C 20 Cycloalkyl, unsubstituted C3-C 20 Cycloalkyl, substituted C3-C 20 Heterocyclic, unsubstituted C3-C 20 Heterocyclic, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloalkynyl or unsubstituted C3-C 20cycloalkynyl, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR and SO3R, wherein R is independently unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted alkylaryl, unsubstituted aryl, unsubstituted C3-C 20 Cycloalkyl, unsubstituted C3-C 20 Heterocyclic, unsubstituted C3-C 20 Cycloalkenyl or unsubstituted C3-C 20 Cycloalkynyl.

[0089] As shown in Formula I, when R 1 When connected to C, the connection can be a bond (single bond, double bond, triple bond), absent, oxygen, sulfur, unsubstituted amino, substituted amino, unsubstituted alkylene, substituted alkylene, unsubstituted alkyl, substituted alkyl, substituted carbonyl, unsubstituted carbonyl, substituted carboxyl, unsubstituted carboxyl, substituted amide, unsubstituted amide, substituted sulfonyl, unsubstituted sulfonyl, substituted sulfonic acid, unsubstituted sulfonic acid, substituted phosphoryl, unsubstituted phosphoryl, substituted phosphonyl or unsubstituted phosphonyl. Preferably, R 1 The connection between A and C is a single bond.

[0090] In some forms, the compound has the structure: in: M is a first row transition metal (e.g., scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc), preferably, M is nickel or copper; X, Y and Z are independently nitrogen or carbon; A, B and C are phenyl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted heterocyclic or substituted heterocyclic ring derivatives, wherein the dotted line represents R 1 Optionally connected to C or not, preferably, R 1 not connected to C; preferably, ring A, B and C are independently benzene, phenyl derivatives, unsubstituted heteroaryl, substituted heteroaryl, heteroaryl derivatives, unsubstituted heterocycle, substituted heterocycle or heterocycle derivatives (each optionally independently having one or more unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted aryl, unsubstituted cycloalkyl, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SOR, halogen, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl or unsubstituted heterocyclyl, wherein R is independently unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted alkaryl, unsubstituted aryl or unsubstituted cycloalkyl); R 1 is any carbon or heteroatom donor ligand, halide or pseudohalide, which may be anionic or neutral. 1 is selected from, but not limited to, unsubstituted alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, , alkynyl, substituted alkynyl, alkoxy, amide, thiolate, phosphide, chloride, bromide, iodide, cyanate, thiocyanate, cyanide, isocyanide, or N-heterocyclic carbene; and n is 0, a positive integer, or a negative integer.

[0091] Preferably, the transition metal atom (M) is nickel, cobalt, copper or iron. More preferably, M is nickel (II), cobalt (I), copper (III) or iron (II). Most preferably, M is nickel (II).

[0092] In some forms, M has d 6 ,d 7 or 8 Electronic configuration, most preferably d 8 .

[0093] In some forms, M has an oxidation state of +2. In some forms, M has an oxidation state of zero (0). In some forms, M has an oxidation state of +1. In some forms, M has an oxidation state of +3.

[0094] In some forms, A, B, and C are independently unsubstituted heteroaryl, substituted heteroaryl, unsubstituted aryl, or substituted aryl.

[0095] In some forms, at least one of A, B and C is a six-membered unsubstituted heteroaryl, a six-membered substituted heteroaryl, a six-membered unsubstituted aryl or a six-membered substituted aryl. In some forms, A, B and C are independently a six-membered unsubstituted heteroaryl, a six-membered substituted heteroaryl, a six-membered unsubstituted aryl or a six-membered substituted aryl.

[0096] In some forms, A, B and C are each independently unsubstituted heteroaryl, substituted heteroaryl, unsubstituted aryl, substituted aryl, unsubstituted polyheteroaryl, substituted polyaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, substituted cycloalkyl, unsubstituted cycloalkyl, substituted heterocyclyl, unsubstituted heterocyclyl, substituted cycloalkenyl, unsubstituted cycloalkenyl, substituted cycloalkynyl or unsubstituted cycloalkynyl, wherein, preferably, the bond between at least one of A, B and C and M is a metal-carbon σ-bond.

[0097] In some forms, R 1is unsubstituted heteroaryl (carbazole), substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, substituted aryl (4-tert-butylphenyl), unsubstituted aryl (phenyl), substituted C3-C 20 Heterocyclic group (substituted C3 heterocyclic group such as 1,3-dimethyl-2,3-dihydro-1H-imidazol-2-yl), unsubstituted C3-C 20 Heterocyclic group (1,3-dimethyl-2,3-dihydro-1H-imidazol-2-yl), substituted N-alkylidene arylamine (2,6-dimethyl-N-methylidene benzylamine), unsubstituted N-alkylidene arylamine (2,6-dimethyl-N-ethylidene benzylamine), unsubstituted arylalkynyl (phenylethynyl), substituted arylalkynyl (4-tert-butylphenylethynyl), unsubstituted alkenyl (vinyl), substituted alkenyl (3,3-dimethylbutenyl, 2-phenylvinyl), unsubstituted arylalkenyl (2-phenylvinyl), substituted arylalkenyl (2-(3,5-di-tert-butylphenyl)vinyl), unsubstituted heteroaryl (pyridin-4-yl), substituted heteroaryl (2,6-dimethylpyridin-4-yl), halogen (chlorine, fluorine, bromine) , iodine), cyano, substituted cyano, cyanate, isocyanate, isothiocyanate, thiocyanate, substituted amino (N,N-diarylamine such as N,N-diphenylamine), unsubstituted amino, phosphide, substituted phosphino (diarylphosphino such as diphenylphosphino), unsubstituted phosphino, hydroxy, unsubstituted aryloxy (phenoxy), substituted aryloxy, unsubstituted arylthio (phenylthio), substituted arylthio, unsubstituted arylseleno (phenylseleno), substituted arylseleno, unsubstituted arylsilyl (triarylsilyl such as triphenylsilyl), substituted arylsilyl, unsubstituted arylboryl (diarylboryl such as diphenylboryl), substituted arylboryl, sulfonate (trifluoromethanesulfonate) or N-heterocyclic carbene.

[0098] In some forms, R 1 is unsubstituted heteroaryl (carbazole), substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, substituted aryl (4-tert-butylphenyl), unsubstituted aryl (phenyl), substituted C3-C 20Heterocyclic group (substituted C3 heterocyclic group such as 1,3-dimethyl-2,3-dihydro-1H-imidazol-2-yl), substituted N-alkylidene arylamine (2,6-dimethyl-N-methylbenzylamine), unsubstituted arylalkynyl (phenylethynyl), substituted arylalkynyl (4-tert-butylphenylethynyl), unsubstituted alkenyl (vinyl), substituted alkenyl (3,3-dimethylbutenyl, 2-phenylvinyl), unsubstituted arylalkenyl (2-phenylvinyl), substituted arylalkenyl (2-(3,5-di-tert-butylphenyl)vinyl), unsubstituted heteroaryl (pyridin-4-yl), substituted heteroaryl (2, 6-dimethylpyridin-4-yl), halogen (chlorine, fluorine, bromine, iodine), cyano, substituted cyano, cyanate, isocyanate, isothiocyanate, thiocyanate, substituted amino (N,N-diarylamine such as N,N-diphenylamine), phosphide, substituted phosphino (diarylphosphino such as diphenylphosphino), hydroxyl, unsubstituted aryloxy (phenoxy), unsubstituted arylthio (phenylthio), unsubstituted arylselenyl (phenylselenyl), unsubstituted arylsilyl (triarylsilyl such as triphenylsilyl), unsubstituted arylboryl (diarylboryl such as diphenylboryl) or sulfonate (trifluoromethanesulfonate).

[0099] In some forms, R 1 is an unsubstituted heteroaryl group (carbazole), a substituted heteroaryl group, an unsubstituted polyheteroaryl group, a substituted polyheteroaryl group or a halogen.

[0100] As shown in Formula II, when R 1 When connected to C, the connection can be a bond (single bond, double bond, triple bond), absent, oxygen, sulfur, unsubstituted amino, substituted amino, unsubstituted alkylene, substituted alkylene, unsubstituted alkyl, substituted alkyl, substituted carbonyl, unsubstituted carbonyl, substituted carboxyl, unsubstituted carboxyl, substituted amide, unsubstituted amide, substituted sulfonyl, unsubstituted sulfonyl, substituted sulfonic acid, unsubstituted sulfonic acid, substituted phosphoryl, unsubstituted phosphoryl, substituted phosphonyl or unsubstituted phosphonyl. Preferably, R 1 The connection between A and C is a single bond.

[0101] In some forms, the compound exhibits photoluminescence or electroluminescence. In some forms, the compound emits light at room temperature, cryogenic temperature, or both. The compound can be in a solid state, liquid state, glass state, or solution state.

[0102] In some forms, the photoluminescent properties of the compounds may be in the spectral range of 380 nm to 1,050 nm, inclusive.

[0103] In some forms, the compound emits light in response to (i) the passage of an electric current or (ii) an electric field. In some forms, the compound emits light independent of its concentration.

[0104] In some forms of the above compounds encompassed by Formula I or Formula II, C is not 1 connect.

[0105] Generally, A, B and C of Formula I or Formula II of the cyclometallated ligand can independently be unsubstituted heteroaryl, substituted heteroaryl, unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, unsubstituted C3-C 20 Cycloalkyl, substituted C3-C 20 Cycloalkyl, unsubstituted C3-C 20 Heterocyclic, substituted C3-C 20 Heterocyclic, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkynyl or substituted C3-C 20 Cycloalkynyl, our preferred substituents should all be included. The introduction of electron withdrawing groups on the pyridine portion will result in a red shift in the emission band. Conversely, the introduction of electron withdrawing groups on the phenyl portion of the cyclometallated ligand will cause a blue shift in the emission band. Similar phenomena can be observed by using electron accepting auxiliary ligands to change the excited state properties of the complex. This color adjustment strategy can also be reflected by complex 1-269 shown below.

[0106] In some forms, the compound has the structure:

[0107] Also described is a light-emitting device having an ordered structure, the light-emitting device comprising an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode, wherein the light-emitting layer comprises a light-emitting compound as described above for Formula I. Figure 7 , the light-emitting device may include (i) a cathode 110, which preferably includes an aluminum layer 120 and a lithium layer 130; (ii) optionally, an electron transport layer 140, which preferably contains 1,3,5-tri(m-pyridin-3-ylphenyl)benzene; (iii) optionally, a carrier confinement layer 150, which preferably contains tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane (3TPYMB); (iv) a light-emitting layer 160, which preferably contains MCP and any light-emitting compound described above for Formula I, such as Compound 2; (v) optionally, a hole transport layer 170, which preferably contains poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS); and (vi) an anode 180, which preferably contains indium tin oxide-coated glass.

[0108] In some forms, the light emitting device contains an electron transport layer and a hole transport layer.

[0109] In some forms of light-emitting devices, the light-emitting layer is formed by doping a light-emitting compound as a dopant into a host compound, and the light-emitting compound has a percentage composition of about 5 wt % to 50 wt %, for example, 10 wt % of the light-emitting layer.

[0110] In some forms, the light-emitting layer contains a host compound selected from, but not limited to, MCP, 4,4'-bis(carbazole-9-yl)biphenyl (CBP), 4,4',4"-tris(carbazole-9-yl)-triphenylamine (TCTA), 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,butylphenyl-1,2,4-triazole (TAZ), p-bis(triphenylsilyl)benzene (UGH2) and diphenyl-4-triphenylsilylphenyl-phosphine oxide (TSPO1). In some forms, the light-emitting layer has a thickness of about 10 nm to 60 nm, for example 30 nm.

[0111] In some forms, the hole transport layer contains an organic compound, which can be, but is not limited to, 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-xylyl-amino)phenyl]cyclohexane (TAPC). In addition, polymeric hole transport materials can be used, which include poly(N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline and copolymers including PEDOT:PSS. In some forms, the thickness of the hole transport layer is about 10 nm to 70 nm, for example 40 nm.

[0112] In some forms, the electron transport layer contains an organic compound, which can be, but is not limited to, 1,3,5-tris(phenyl-2-benzimidazolyl)-benzene (TPBI), 1,3,5-tris[(3-pyridyl)-phenyl-3-yl]benzene (TmPyPB), bathocuproin (BCP), bathophenanthroline (BPhen) and bis(2-methyl-8-hydroxyquinolinolato)-4-(biphenylhydroxy)-aluminum (BAlq), 1,3,5-tris[(3-pyridyl)-phenyl-3-yl]benzene (TmPyPB), 1,3-bis[3,5-di(pyridin-3-yl)-phenyl]benzene (BmPyPhB) and 1,3,5-tris(6-(3-(pyridin-3-yl)phenyl)pyridin-2-yl)benzene (Tm3PyP26PyB). In some forms, the electron transport layer has a thickness of about 10 nm to 60 nm, such as 40 nm.

[0113] In some forms, the light-emitting device contains a carrier confinement layer inserted between the hole transport layer and the light-emitting layer or between the light-emitting layer and the electron transport layer. Preferably, the carrier confinement layer improves the performance of the light-emitting device. In some forms, the carrier confinement layer contains an organic compound, which can be but is not limited to CBP, TCTA, 3TPYMB, BmPyPhB and Tm3PyP26PyB. In some forms, the thickness of the carrier confinement layer is about 5nm to about 50nm, for example 10nm.

[0114] Preferably, the anode of the light emitting device contains indium tin oxide coated glass. Preferably, the cathode of the light emitting device contains lithium fluoride, aluminum or a combination thereof. In some forms, the lithium fluoride forms a layer with a thickness of about 0.05nm to 5nm (such as 1nm). In some forms, the aluminum forms a layer with a thickness of about 50nm to about 250nm (such as 150nm).

[0115] Each compound within the above definition is intended and should be considered to be explicitly disclosed herein. In addition, each subgroup that can be identified within the above definition is intended and should be considered to be explicitly disclosed herein. Therefore, it is explicitly considered that any compound or subgroup of compounds can be specifically included or excluded for use, or included in or excluded from the list of compounds. For example, any one or more compounds described herein having a structure depicted herein or mentioned in the tables or examples herein can be specifically included, excluded, or combined in any combination in a group or subgroup of such compounds. Such specific groups, subgroups, inclusions and exclusions can be applied to any aspect of the compositions and methods described herein. For example, a group of compounds that specifically excludes one or more specific compounds can be used or applied in the context of the compound itself (e.g., a list or group of compounds), a composition containing the compound, any one or more of the disclosed methods, or a combination of these. Different groups and subgroups of compounds with such specific inclusions and exclusions can be used or applied in the context of the compound itself, a composition containing one or more compounds, or any disclosed method. All of these different groups and subgroups of compounds - as well as different groups of compounds, compositions, and methods of using or applying the compounds - are specifically and individually contemplated and should be considered to be specifically and individually described. For example, the following may be specifically included or excluded from any compound per se (e.g., a list or group of compounds), a composition comprising the compound, or any one or more disclosed methods, or a combination of these as a group or individually. For example, compounds of Formula I or Formula II may exclude any complex containing a tetradentate ligand described in U.S. Patent Application Publication 2018 / 0194790 to Li et al. For example, in certain forms of Formula I, where p is 1 and C is R 1 Connections, A, B, C and R 1 is not a substituted polyheteroaryl, an unsubstituted polyheteroaryl, a substituted polyaryl or an unsubstituted polyaryl. In another example, in certain forms of Formula I, wherein p is 1 and C and R 1 connected, and M is cobalt, copper, nickel, manganese or zinc, R 1 M is not a substituted polyheteroaryl, an unsubstituted polyheteroaryl, a substituted polyaryl, or an unsubstituted polyaryl. As another example, M may exclude Pt 2+ , Pd 2+ , Ir 3+ and / or Au 3+ As a further example, any one or combination of first row transition metals may be excluded.

[0116] III. Preparation Methods (A) Transition Metal Complexes The transition metal complexes and their ligands described herein can be synthesized using methods known in the field of organic chemical synthesis. For example, the tridentate ligands N^C^N and 3-CF3-N^C(tBu)^N-CF3-3, and the corresponding precursor compounds [Ni(N^C^N)Cl] and [Ni(3-CF3-N^C(tBu)^N-CF3-3)Cl] can be prepared by modifying the procedures reported in the literature [Soro, B.; Stoccoro, S.; Minghetti, G.; Zucca, A.; Cinellu, MA; Gladiali, S.; Manassero, M.; Sansoni, M. Organometallics 1, 53 (2005)]. In addition, ligands with desired dentate (e.g., tridentate and tetradentate) can be synthesized according to the methods described in Turner "Luminescent cyclometalated platinum and palladium complexes with novel photophysical properties" Diss. 2014 and Cheng, [Cheng, G.; Kui, SCF; Ang, W.-H.; Ko, M.-Y.; Chow, P.-K.; Kwong, C.-L.; Kwok, C.-C.; Ma, C.; Guan, X.; Low, K.-H.; Su, S.-J.; Che, C.-M. Chem. Sci. 5, 4819 (2014)]. The target transition metal complex can be synthesized by reacting the corresponding precursor compound with the corresponding auxiliary ligand in an organic solvent in the presence of a suitable base. Specific transition metal complexes such as those containing nickel (II) are disclosed in the examples.

[0117] (B) Organic Light Emitting Device Also described are methods of making OLEDs containing one or more transition metal complexes described above for Formula I. Preferred methods of making OLEDs include vacuum deposition or solution processing techniques, such as spin coating and inkjet printing. In the Examples a method of making an OLED comprising a transition metal complex described herein is disclosed.

[0118] IV. How to use Preferably, the transition metal complexes described herein are photostable and emit at room temperature, low temperature, or a combination thereof. Thus, the compounds described herein can be incorporated into OLEDs and used in commercial applications such as smartphones, televisions, monitors, digital cameras, tablets, and lighting fixtures (which typically operate at room temperature).

[0119] The methods, compounds and compositions described herein are further illustrated in the following examples, which are provided by way of illustration and are not intended to be limiting. It should be understood that changes in the proportions of the components shown and substitutions of the elements are obvious to those skilled in the art and are within the scope of the disclosed forms. Theoretical aspects are presented with the understanding that the applicant is not attempting to be bound by the proposed theory. Unless otherwise stated, all parts or amounts are by weight. Example

[0120] Example 1: Synthesis and characterization of compounds Materials and methods 2-Bromopyridine (Sigma-Aldrich), 1,3-dibromobenzene (Sigma-Aldrich), zinc bromide (Sigma-Aldrich), lithium chloride (Sigma-Aldrich), tetrakis(triphenylphosphine)palladium (Sigma-Aldrich), carbazole (Sigma-Aldrich), n-butyllithium (Sigma-Aldrich), sodium hydroxide (J&K Chemical), 2-(tributylstannyl)pyridine (Sigma-Aldrich), nickel(II) chloride (Sigma-Aldrich), nickel(II) acetate (Sigma-Aldrich), mercuric(II) acetate (Sigma-Aldrich), 7-bromo-1-tetralone (Sigma-Aldrich), potassium tert-butoxide (Sigma-Aldrich), ammonium acetate (Sigma-Aldrich), sodium fluoride (NaF) (Sigma-Aldrich), and boron tribromide (BBr3) (AlfaAesar) were purchased from the corresponding chemical companies.

[0121] (i) Synthesis and characterization of compounds Schematic diagrams of the synthesis of tridentate and tetradentate compounds are shown below in Schemes 1 and 2, respectively.

[0122] Solution 1: In this diagram: R 1 R may be selected from, but is not limited to, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocyclic aryl, substituted heterocyclic aryl, alkynyl, or substituted alkynyl. 1 It may also be a group having a heteroatom as a donor atom, selected from but not limited to nitrogen, oxygen, sulfur or phosphorus; Rings A, B and C are independently benzene, a phenyl derivative, a heterocycle or a heterocycle derivative, but are not limited to having 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, SOR, halogen, aryl, substituted aryl, heteroaryl, substituted heteroaryl or heterocyclyl, wherein R is independently alkyl, alkenyl, alkynyl, alkaryl, aryl or cycloalkyl; and n is 0, a positive integer, or a negative integer.

[0123] Solution 2: In this diagram: Rings A, B, C and D are independently benzene, a phenyl derivative, a heterocycle or a heterocycle derivative, but are not limited to having 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, SOR, halogen, aryl, substituted aryl, heteroaryl, substituted heteroaryl or heterocyclyl, wherein R is independently alkyl, alkenyl, alkynyl, alkaryl, aryl or cycloalkyl; and X may be selected from, but not limited to, O, S, Se, NR, CR2, SiR2, wherein R is independently alkyl, alkenyl, alkynyl, alkaryl, aryl or cycloalkyl; and n is 0, a positive integer, or a negative integer.

[0124] (a) Synthesis of tridentate ligands N^C^N and 3-CF3-N^C(tBu)^N-CF3-3 and precursor compounds [Ni(N^C^N)Cl] and [Ni(3-CF3-N^C(tBu)^N-CF3-3)Cl] according to the literature [Soro, B.; Stoccoro, S.; Minghetti, G.; Zucca, A.; Cinellu, MA; Gladiali, S.; Manassero, M.; Sansoni, M. Organometallics 1, 53 (2005)], while the tetradentate ligand N^C^N^O was prepared according to the modification of the procedure reported in the literature [Cheng, G.; Kui, S. C. F.; Ang, W.-H.; Ko, M.-Y.; Chow, P.-K.; Kwong, C.-L.; Kwok, C.-C.; Ma, C.; Guan, X.; Low, K.-H.; Su, S.-J.; Che, C.-M. Chem. Sci. 5, 4819 (2014)]. For the tridentate ligand, the target compound was synthesized by reacting [Ni(N^C^N)Cl] with the corresponding carbazole ligand in the presence of a base in an organic solvent. For example, compound 2 as shown herein was synthesized by stirring a mixture of [Ni(N^C^N)Cl] (100 mg, 0.31 mmol), carbazole (103 mg, 0.62 mmol) and NaOH (61.7 mg, 1.55 mmol) in MeOH / CH2Cl2 (1:1, v / v) at 80°C under an inert atmosphere overnight. The orange suspension was then separated by filtration, and the solid was washed successively with deionized water, methanol and ether to obtain a yellow-orange solid. The product was recrystallized by diffusing ether vapor into a concentrated dichloromethane solution to obtain a yellow solid. Yield: 0.11 g, 80%. For the tetradentate complex, the target compound was synthesized by reacting the tetradentate ligand with nickel (II) acetate in the presence of acetic acid under reflux. The chemical structure of compound 1-269 is shown herein.

[0125] (b) Characterizing compounds 1-4, wherein the characterization is as follows: Compound 1: [Ni(N^C^N)Cl]. Yellow solid. Yield: 90 mg, 60%. 1 H NMR (400 MHz, acetone-d 6, 298K, δ / ppm): δ9.06(d,J=8.0Hz,2H),8.04(t,J=8.0Hz,2H),7.84(d,J=8.0 Hz, 2H), 7.52 (d, J = 8.0 Hz, 2H), 7.32 (t, J = 8.0 Hz, 2H), 7.21 (t, J = 8.0 Hz, 2H).13 C{ 1 H}NMR (150 MHz, acetone-d 6, 298K,δ / ppm):δ172.07,164.28,154.54,145.55,140.75,125.97,123.73,123.57,119.35. Positive ion MALDI-MS:m / z 289.031[M-Cl] + ,323.997[M] + ,366.054[M+CH3CN+H] + .

[0126] Compound 2: [Ni(N^C^N)(Cbz)]. Yellow solid. Yield: 110 mg, 80%. 1 H NMR (400 MHz, acetone-d 6, 298K, δ / ppm): δ8.21(d,J=8.0Hz,2H),8.15(t,J=8.0Hz,2H),7.76(dt,J=8.0Hz,2H),7.61(d,J=8.0Hz,2H ),7.44(d,J=4.0Hz,2H),7.24-7.31(m,3H),7.03(dt,J=8.0Hz,2H),6.95-6.97(m,2H),6.70-6.74(m,2H). 13 C{ 1 H}NMR (150 MHz, acetone-d 6, 298K,δ / ppm):δ175.76,164.93,153.28,150.72,145.47,139.66,126.23,125.76,124.18,123.53,122.83,120.14,118.71,115.56,114.91. Positive ion MALDI-MS:m / z 454.951[M] + ,497.063[M+CH3CN+H] + .

[0127] Compound 3: [Ni(3-CF3-N^C( t Bu)^N-CF3-3)Cl]. Red solid. Yield: 98 mg, 70%. 1 H NMR (400 MHz, dichloromethane-d 2, 298K, δ / ppm): δ9.37 (s, 2H), 8.05 (dd, J = 8.0Hz, 2H), 7.68 (d, J = 8.0Hz, 2H), 7.47 (s, 2H), 1.41 (s, 9H). 13 C{1 H}NMR (150 MHz, acetone-d 6, 298K,δ / ppm):δ169.64,165.96,151.21,149.49,142.85,136.16,125.73,125.46,123.63,121.71,121.46,117.58,35.16,31.49. Positive ion MALDI-MS:m / z 497.063[M-Cl] + .

[0128] Compound 4: [Ni(N^C^N^O)]. Red solid. Yield: 110 mg, 50%. 1 H NMR (500 MHz, dichloromethane-d2, 298 K, δ / ppm): δ8.73 (d, J=7.8 Hz, 1H), 7.96 (d, J=7.4 Hz, 1H), 7.88–7.84 (m, 2H), 7.66 (d, J=8.4 Hz, 1H), 7.54 (d, J=7.8 Hz, 1H), 7.28–7.24 (m, 2H), 7.21 (t, J=7.4 Hz, 1H), 7.12 (d, J=7.8 Hz, 1H), 6.86 (d, J=7.4 Hz, 1H), 6.66 (t, J=7.4 Hz, 1H), 3.18–3.14 (m, 2H), 3.08–3.04 (m, 2H). 13 C{ 1 H}NMR (150MHz, dichloromethane-d2, 298K, δ / ppm): δ176.41, 165.27, 164.70, 158.88, 153.26, 150.44, 141.96, 141.53, 139.31, 136.75, 135.42, 131.30, 127.89, 125.91, 124.92, 122.79, 122.30, 122.23, 120.23, 119.13, 118.67, 114.54, 27.07, 26.25. Positive ion HR-ESI-MS: m / z 406.0589 [M] + . C 24 H 16 Elemental analysis calculated value (%) of N2NiO·2CH2Cl2: C, 54.13; H, 3.49; N, 4.86. Found value: C, 54.57; H, 3.55; N, 5.13.

[0129] Example 2: Absorption properties of compounds Materials and methods Spectroscopic grade dichloromethane (J&K Chemical) and spectroscopic grade toluene (Sigma-Aldrich) were purchased and used without further purification.

[0130] The UV-visible absorption data of compounds 1-4 in dichloromethane at 298 K are summarized in Table 1. The UV-visible absorption spectra of compounds 1 and 3 in dichloromethane at 298 K are characterized by broad and strong absorption bands at about 270–320 nm with extinction coefficients (ε) of 10 4 dm 3 mol –1 cm –1 of magnitude, such as Figure 1 As shown. This absorption band is tentatively assigned to the intra-ligand (IL)π→π* transition of the cyclometalated N^C^N ligand. A moderately intense absorption band at about 350–450 nm is also observed, which is tentatively assigned to be mainly metal-to-ligand charge transfer (MLCT) [dπ(Ni)→π*(N^C^N)] with some halide-to-N^C^N ligand-to-ligand charge transfer (LLCT) features [Shields, BJ; Kudisch, B.; Scholes, GD; Doyle, AGJ Am. Chem. Soc. 140, 3035 (2018); Klein, A.; Rausch, B.; Kaiser, A.; Vogt, N.; Krest, AJ Organomet. Chem. 774, 86 (2014)]. On the other hand, carbazolyl nickel (II) complex 2 shows a strong absorption band at about 270-350 nm, which is attributed to the ILπ→π* transition of the cyclometallated N^C^N ligand. A moderately strong absorption band at about 350-470 nm is also observed. This absorption band is assigned to be mainly MLCT [dπ(Ni)→π*(N^C^N)], mixed with some LLCT [π(carbazolate)→π*(N^C^N)] transition. For 4, similar to 1 and 2, a strong absorption band at about 270-350 nm is observed, while the absorption band at λ≤350 nm is attributed to the spin-allowed intra-ligand IL[π→π*] transition of the cyclometallated N^C^N^O ligand of 4. A moderately intense absorption band of 4 at approximately 350–400 nm was observed, tentatively assigned to the MLCT [dπ(Ni)π→π*(N^C^N^O)] transition mixed with intraligand charge transfer (ILCT) transition from the phenolic moiety to the pyridinyl moiety of the N^C^N^O ligand, while the lowest energy absorption band could be assigned to a mixture of the metal center (MC) and ILCT transfer transition from the phenolic moiety to the pyridinyl moiety of the N^C^N^O ligand.

[0131] Table 1. Absorption data of compounds 1-4

[0132] Example 3: Emission properties of compounds Materials and methods Spectroscopic grade dichloromethane (J&K Chemical) and spectroscopic grade toluene (Sigma-Aldrich) were purchased and used without further purification.

[0133] The emission properties of compounds 1-4 are summarized in Table 2. Unlike most other square-planar nickel (II) compounds [Shields, BJ; Kudisch, B.; Scholes, GD; Doyle, AGAm. Chem. Soc. 140, 3035 (2018); Klein, A.; Rausch, B.; Kaiser, A.; Vogt, N.; Krest, AJ Organomet. Chem. 774, 86 (2014)], compounds 1-3 show luminescence in solution at room temperature. The emission spectra of compounds 1 and 3 in degassed dichloromethane solutions are shown in Table 2. Figure 2 Upon excitation at λ = 400 nm in dichloromethane solution at 298 K, unstructured emission bands of 1 and 3 were observed with a maximum peak at about 500 nm, where the broad and unstructured emission bands were tentatively assigned as 3 MLCT excited state. When excited at λ = 360 nm at 298 K, compound 2 shows an emission band with an electronic vibration structure in a degassed toluene solution, with a maximum peak at about 500 nm and a vibration asymptotic interval of about 1300 cm -1 , with the tridentate ligand ν(C … C) and ν(C … N) The stretching mode matches well, indicating that the emitted metallic disturbance 3 ILπ→π* state, such as Figure 3 In addition, when excited at λ = 360 nm, compound 2 is characterized by an emission band of an electronic vibration structure in the solid state at 77 K, and an emission band of an unstructured structure in the solid state at 298 K, as shown in FIG. Figure 4 and Figure 5 As shown. For 77 K, the emission energy is very similar to that in degassed toluene solution at 298 K. In addition, the emission properties of compound 2 in solid-state MCP films have been investigated. Figure 6 The normalized photoluminescence spectra of a thin film of 10 wt% compound 2 doped into MCP at 298 K are depicted, where compound 2 shows an unstructured emission band with a maximum peak at about 600 nm.

[0134] Table 2. Emission data of compounds 1-4

[0135] Example 4: Organic Light Emitting Device Materials and methods PEDOT:PSS (Clevious AI4083) was purchased from Heraeus Ltd and filtered with a 0.2 μm nylon filter before use. 3TPyMB, MCP, TmPyPB were purchased from Luminescence Technology Corp., while LiF and Al were purchased from Sigma-Aldrich and Good Fellow, respectively. All materials were used without further purification.

[0136] Solution-processable OLEDs are constructed as follows: (a) A transparent anodized indium tin oxide (ITO)-coated borosilicate glass substrate (38 mm × 38 mm) with a sheet resistance of 30 Ω / □ was ultrasonically treated in a commercial detergent Decon 90, rinsed in deionized water with a resistivity of 18.2 MΩ for 15 minutes, and then dried in an oven at 120°C for at least 1 hour. Next, the substrate was UV-ozone treated for 15 minutes in a Jelight 42-220 UVO cleaner equipped with a mercury barrier lamp to increase the work function of the ITO-coated glass substrate for better hole injection into the organic layer.

[0137] (b) A 40 nm thick PEDOT:PSS hole transport layer was spin coated onto the ITO-coated glass substrate of step (a) using a Laurell WS-400Ez-6NPP-Lit2 single wafer spin handler at 7000 rpm for 30 seconds and baked at 110 °C in air for 10 minutes.

[0138] (c) A 30 nm thick light-emitting layer was spin coated onto the PEDOT:PSS layer of step (b) using a Laurell WS-400Ez-6NPP-Lit2 single wafer spin handler at 6000 rpm for 25 seconds and baked at 80°C in air for 10 minutes, wherein 10 wt% of compound 2 was doped into the light-emitting MCP layer.

[0139] (d) The substrate was placed in a vacuum chamber and the chamber was evacuated from 1 bar to 5 × 10 –6 millibar.

[0140] (e) A 5 nm thick 3TPYMB carrier confinement layer was deposited on the doped MCP light-emitting layer of step (c) by thermal evaporation.

[0141] (f) A 40 nm TmPyPB electron transport layer was deposited on the 3TPYMB layer of step (e) by thermal evaporation.

[0142] (g) A 1 nm thick LiF layer and a 150 nm thick Al layer were deposited on the TmPyPB layer of step (f) by thermal evaporation to form an electron injection cathode.

[0143] Figure 7 The EL spectra of devices based on doping 10 wt% of compound 2 in MCP as the light-emitting layer are depicted. Strikingly, a broad EL spectrum is observed with increasing operating voltage, with an emission peak at about 600 nm. This red emission is very consistent with the photoluminescence spectrum in the film and comes from compound 2. Although undesired exciplex emission at about 440 nm is noted, which may be due to poor energy transfer from MCP to the nickel (II) compound, this finding demonstrates the first class of luminescent nickel (II) compounds that emit at room temperature and their potential application in OLEDs.

[0144] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention belongs.Publications cited herein and the materials for which they are cited are specifically incorporated by reference.

[0145] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the appended claims.

Claims

1. A luminescent compound having the formula: in: The compound has an overall negative charge, is neutral, or has a positive charge; M is a first row transition metal atom, preferably M is nickel, copper, iron or cobalt, most preferably M is nickel; M has an oxidation state of 0 to +7, inclusive, preferably an oxidation state of 0, +1, +2 or +3; A, B and C are each independently unsubstituted heteroaryl, substituted heteroaryl, unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, substituted C3-C 20 Cycloalkyl, unsubstituted C3-C 20 Cycloalkyl, substituted C3-C 20 Heterocyclic, unsubstituted C3-C 20 Heterocyclic, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloalkynyl, or unsubstituted C3-C 20 Cycloalkynyl, preferably, at least one of A, B and C is substituted aryl or unsubstituted aryl, and the other of A, B and C is substituted heteroaryl or unsubstituted heteroaryl, preferably, the bond between at least one of A, B and C and M is a metal-carbon sigma bond; wherein the dotted line represents R 1 Optionally connected to C or not, preferably, R 1 Not connected to C; q is 1 or 2, preferably 1; p is 1 (tridentate ligand), 2 (tetradentate ligand), or 3 (pentadentate ligand), preferably 1 (tridentate ligand) and 2 (tetradentate ligand); G and J are each independently a bond (single bond, double bond, triple bond), absent, oxygen, sulfur, unsubstituted amino, substituted amino, unsubstituted alkylene, substituted alkylene, unsubstituted alkyl, substituted alkyl, substituted carbonyl, unsubstituted carbonyl, substituted carboxyl, unsubstituted carboxyl, substituted amide, unsubstituted amide, substituted sulfonyl, unsubstituted sulfonyl, substituted sulfonic acid, unsubstituted sulfonic acid, substituted phosphoryl, unsubstituted phosphoryl, substituted phosphonyl, or unsubstituted phosphonyl; preferably, G and J are each a single bond; R 1 is a carbon or heteroatom donor ligand, a halide or pseudohalide, which may be monoanionic or neutral, such as unsubstituted heteroaryl (carbazole), substituted heteroaryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, substituted aryl (4-tert-butylphenyl), unsubstituted aryl (phenyl), substituted C3-C 20 Heterocyclic group (substituted C3 heterocyclic group, such as 1,3-dimethyl-2,3-dihydro-1H-imidazol-2-yl), unsubstituted C3-C 20 heterocyclic group (2,3-dihydro-1H-imidazol-2-yl), substituted N-alkylidene arylamine (2,6-dimethyl-N-methylidene benzylamine), unsubstituted N-alkylidene arylamine (2,6-dimethyl-N-ethylidene benzylamine), unsubstituted arylalkynyl (phenylethynyl), substituted arylalkynyl (4-tert-butylphenylethynyl), unsubstituted alkyl, substituted alkyl, unsubstituted alkynyl, substituted alkynyl, unsubstituted alkene alkyl (vinyl), substituted alkenyl (3,3-dimethylbutenyl, 2-phenylvinyl), unsubstituted arylalkenyl (2-phenylvinyl), substituted arylalkenyl (2-(3,5-di-tert-butylphenyl)vinyl), unsubstituted heteroaryl (pyridin-4-yl), substituted heteroaryl (2,6-dimethylpyridin-4-yl), halogen (chlorine, fluorine, bromine, iodine), cyano, substituted cyano, cyanate, isocyanate, isothiocyanate, thiocyanate cyanate, substituted amino (N,N-diarylamine, such as N,N-diphenylamine), unsubstituted amino, phosphide, substituted phosphino (diarylphosphino, such as diphenylphosphino), unsubstituted phosphino, hydroxy, unsubstituted alkoxy, substituted alkoxy, unsubstituted amide, substituted amide, unsubstituted aryloxy (phenoxy), substituted aryloxy, unsubstituted arylthio (phenylthio), substituted arylthio, unsubstituted arylselenyl (phenylselenyl), substituted arylselenyl, unsubstituted arylsilyl (triarylsilyl, such as triphenylsilyl), substituted arylsilyl, unsubstituted arylboryl (diarylboryl, such as diphenylboryl), substituted arylboryl, unsubstituted alkylboryl, substituted alkylboryl, unsubstituted boryl, substituted boryl, sulfonate (trifluoromethanesulfonate), or N-heterocyclic carbene; r is 0, 1, or 2, preferably, r is 1, and optionally, wherein substituted refers to substitution by one or more substituents selected from unsubstituted alkyl, alkyl (tert-butyl) having one or more alkyl substituents, alkyl (trifluoromethyl) having one or more halogen substituents, halogen (chlorine, fluorine, bromine, iodine), unsubstituted aryl (phenyl), aryl (2,6-dimethylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl) having one or more alkyl substituents, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, substituted C3-C 20 Cycloalkyl, unsubstituted C3-C 20 Cycloalkyl, substituted C3-C 20 Heterocyclic, unsubstituted C3-C 20 Heterocyclic, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloalkynyl, or unsubstituted C3-C 20 cycloalkynyl, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR and SO3R, wherein R is independently unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted alkylaryl, unsubstituted aryl, unsubstituted C3-C 20 Cycloalkyl, unsubstituted C3-C 20 Heterocyclic, unsubstituted C3-C 20 Cycloalkenyl, or unsubstituted C3-C 20 Cycloalkynyl, and optionally, wherein, (i) when p is 1 and C and R 1 When connected, A, B, C and R 1 is not a substituted polyheteroaryl, an unsubstituted polyheteroaryl, a substituted polyaryl, or an unsubstituted polyaryl; or (ii) when p is 1 and C and R 1 When M is cobalt, copper, nickel, manganese or zinc, R 1 It is not a substituted polyheteroaryl, an unsubstituted polyheteroaryl, a substituted polyaryl or an unsubstituted polyaryl.

2. The luminescent compound according to claim 1, which has the following formula: in: M is a first row transition metal (e.g., scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc), preferably, M is nickel or copper; X, Y and Z are independently nitrogen or carbon; A, B and C are phenyl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted heterocyclic or substituted heterocyclic ring derivatives, wherein the dotted line represents R 1 Optionally connected to C or not, preferably, R 1 not connected to C; preferably, ring A, B and C are independently benzene, phenyl derivatives, unsubstituted heteroaryl, substituted heteroaryl, heteroaryl derivatives, unsubstituted heterocycle, substituted heterocycle or heterocycle derivatives (each optionally independently having one or more unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted aryl, unsubstituted cycloalkyl, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SOR, halogen, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl or unsubstituted heterocyclyl, wherein R is independently unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted alkaryl, unsubstituted aryl, or unsubstituted cycloalkyl); R 1 is any carbon or heteroatom donor ligand, halide or pseudohalide, which may be anionic or neutral. Preferably, R 1 is selected from, but not limited to, unsubstituted alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted alkynyl, substituted alkynyl, unsubstituted alkoxy, amide, thiol, phosphide, chloride, bromide, iodide, cyanate, thiocyanate, cyanide, isocyanide, or N-heterocyclic carbene; and n is 0, a positive integer, or a negative integer.

3. The luminescent compound according to claim 1 or 2, wherein M has d 6 ,d 7 , or d 8 Electronic configuration; and / or wherein M has an oxidation state of 0, 1, +2 or +3, preferably an oxidation state of +2; and / or Wherein M is nickel.

4. The luminescent compound according to any one of claims 1 to 3, wherein A, B and C are each independently unsubstituted heteroaryl, substituted heteroaryl, unsubstituted aryl, substituted aryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, unsubstituted polyaryl, substituted polyaryl, substituted cycloalkyl, unsubstituted cycloalkyl, substituted heterocyclyl, unsubstituted heterocyclyl, substituted cycloalkenyl, unsubstituted cycloalkenyl, substituted cycloalkynyl or unsubstituted cycloalkynyl, wherein, Preferably, the bond between at least one of A, B and C and M is a metal-carbon sigma-bond; and / or wherein A, B and C are independently unsubstituted heteroaryl, substituted heteroaryl, unsubstituted aryl or substituted aryl; and / or Where C is not 1 connect.

5. The luminescent compound according to any one of claims 1 to 4, which exhibits photoluminescence or electroluminescence; and / or wherein the luminescent compound has a planar square geometry; and / or wherein the luminescent compound emits light at room temperature, low temperature, or both; and / or wherein the luminescent compound is in a solid state, a liquid state, a glass state or a solution state; and / or wherein the luminescent compound has photoluminescent properties in the spectral range of 380 nm to 1050 nm, the spectral range including 380 nm and 1050 nm; and / or wherein the luminescent compound emits light in response to (i) the passage of an electric current or (ii) an electric field; and / or The luminescent compound emits light independently of its concentration.

6. The luminescent compound according to any one of claims 1 to 5, which is selected from 7. A light-emitting device comprising an anode, a light-emitting layer and a cathode, wherein the light-emitting layer comprises the light-emitting compound according to any one of claims 1 to 6, and optionally a host compound, Preferably, the light-emitting device further comprises an electron transport layer and a hole transport layer; and / or the light-emitting device further comprises a carrier confinement layer, More preferably, the light emitting layer, the electron transport layer, the hole transport layer and the carrier confining layer are located between the anode and the cathode.

8. The light-emitting device of claim 7, wherein the light-emitting layer comprises the light-emitting compound as a dopant of the host compound, wherein the composition percentage of the dopant is about 5wt% to 50wt%, for example 10wt% of the light-emitting layer; and / or wherein the thickness of the light-emitting layer is about 10 nm to 60 nm, for example 30 nm; and / or wherein the light-emitting layer is prepared using vacuum deposition or solution processing techniques; and / or wherein the host compound is selected from 1,3-bis(carbazole-9-yl)benzene (MCP), 4,4'-bis(carbazole-9-yl)biphenyl (CBP), 4,4',4"-tri(carbazole-9-yl)-triphenylamine (TCTA), 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,butylphenyl-1,2,4-triazole (TAZ), p-bis(triphenylsilyl)benzene (UGH2) and diphenyl-4-triphenylsilylphenyl-phosphine oxide (TSPO1), and combinations thereof; and / or wherein the anode comprises indium tin oxide coated glass; and / or The cathode comprises lithium fluoride, aluminum or a combination thereof.

9. A light-emitting device as described in claim 7 or 8, wherein the hole transport layer comprises 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-xylyl-amino)phenyl]cyclohexane (TAPC); polymeric hole transport materials can be used, including poly(N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline and copolymers including poly(3,4-ethylenedioxythiophene):poly(4-styrene-sulfonic acid) (PEDOT:PSS), and mixtures thereof; and / or wherein the thickness of the hole transport layer is about 10 nm to 70 nm, for example 40 nm; and / or The electron transport layer comprises 1,3,5-tris(phenyl-2-benzimidazolyl)-benzene (TPBI), 1,3,5-tris[(3-pyridyl)-phenyl-3-yl]benzene (TmPyPB), bathocuproin (BCP), bathophenanthroline (BPhen) and bis(2-methyl-8-hydroxyquinolinolato)-4-(biphenylhydroxy)-aluminum (BAlq), tris-[2,4,6-trimethyl-3-(pyridyl)-phenyl-3-yl]benzene (TmPyPB), 1,3,5-tris[(3-pyridin-3-yl)phenyl]borane (3TPYMB), 1,3,5-tris[(3-pyridinyl)-phenyl-3-yl]benzene (TmPyPB), 1,3-bis[3,5-di(pyridin-3-yl)-phenyl]benzene (BmPyPhB) and 1,3,5-tris(6-(3-(pyridin-3-yl)phenyl)pyridin-2-yl)benzene (Tm3PyP26PyB), and mixtures thereof; and / or wherein the thickness of the electron transport layer is about 10 nm to 60 nm, for example 40 nm; and / or wherein the carrier confining layer comprises an organic compound, such as tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane (3TPYMB); and / or The thickness of the carrier confinement layer is about 5 nm to about 50 nm, for example, 10 nm.

10. The light emitting device of claim 8, wherein the lithium fluoride forms a layer having a thickness of about 0.05 nm to 5 nm, for example 1 nm; and / or The aluminum forms a layer having a thickness of about 50 nm to about 250 nm, for example 150 nm.

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