TW201441206A - Quinazoline derived compounds for electronic films and devices - Google Patents

Abstract

The invention provides a composition comprising at least one compound selected from the group consisting of the following (A, B, C and D): (A) wherein R1, R2 and R3 are each described herein; and wherein Formula 1 comprises at least three C-N double bonds; and wherein one or more hydrogens may be optionally substituted with deuterium; (B) wherein R1', R2', R3', R4', R5' and L are each described herein, and wherein if R1' comprises a biphenyl, it does not comprises a carbazole; and wherein one or more hydrogens may be optionally substituted with deuterium; (C) wherein R1'', R2'', R3'', R4'' and R5'' are each described; and wherein if R1' comprises a biphenyl, it does not comprises a carbazole; and wherein one or more hydrogens may be optionally substituted with deuterium; and (D) a combination thereof.

Description

Quinazoline derivative compounds for electronic films and components References to relevant applications

This application claims the benefit of U.S. Patent Provisional Application No. 61/798,460, filed on March 15, 2013.

Field of invention

This invention relates to quinazoline derivative compounds for use in electronic films and elements.

Background of the invention

The electroluminescence (EL) element is a display element using a film stack containing an organic aromatic compound as an electroluminescent layer. These compounds are generally classified into electroluminescent materials and charge transport materials. These electroluminescent compounds and charge transporting compounds require several properties, including high fluorescence quantum yield in solid state, high mobility of electrons and holes, chemical stability during vacuum vapor deposition, and the ability to form stable films. These desirable features extend the useful life of the EL element. There is still a continuing need to improve electroluminescent compounds and films containing such compounds.

International Publication No. WO 2012/050347 discloses compounds for use as organic electronic materials, and organic electroluminescent elements using such compounds Pieces. Such compounds are disclosed as having high electron transport capabilities and preventing crystallization from occurring in the manufacture of the component. These compounds are also disclosed as facilitating the formation of layers, and thus improving the properties of current OLED elements. Other compounds for electronic applications are disclosed in the following: WO2011/014039A1, WO2012/036482, WO2006/104118, and EP1808433.

However, as discussed above, there remains a need for novel membrane configurations that contain novel electroluminescent compounds and have improved luminescent properties. These needs and others have been met by the invention described below.

Summary of invention

The present invention provides a composition comprising at least one compound selected from the group consisting of (A, B, C, and D): A) Wherein R1 is selected from the group consisting of: i) (C6-C40) aryl, further (C6-C30) aryl, each with or without a substituent, or ii) (C3-C40)heteroaryl, further (C3-C30)heteroaryl, each with or without a substituent; wherein R2 is selected from the group consisting of: i) (C6-C40) aryl, further (C6-C30) aryl, each with or without a substituent Or ii) (C3-C40)heteroaryl, further (C3-C30)heteroaryl, each with or without a substituent, and wherein R3 is selected from the group consisting of: i) hydrogen or deuterium, ii) ( C1-C20)alkyl, further (C1-C10)alkyl, iii) (C6-C40) aryl, further (C6-C30) aryl, each with or without a substituent, or iv) (C3 a -C40)heteroaryl group, further a (C3-C30)heteroaryl group, each with or without a substituent, and wherein the formula 1 comprises at least three CN double bonds; and one or more of the hydrogens thereof may be selectively deuterated Replace; B) Wherein R1' is selected from the group consisting of: i) (C6-C40) aryl, further (C6-C30) aryl, each with or without a substituent, or ii) (C3-C40)heteroaryl, further Is a (C3-C30)heteroaryl group, each with or without a substituent; wherein R2' is selected from the group consisting of: i) hydrogen or hydrazine, ii) (C1-C20) alkyl, further (C1-C10) alkane a group, iii) (C6-C40) aryl, further (C6-C30) aryl, each with or without a substituent, or iv) (C3-C40)heteroaryl, further (C3-C30) Aryl groups, each with or without a substituent; wherein R3' and R4' are independently selected from the group consisting of: i) hydrogen or hydrazine, ii) (C1-C20) alkyl group, further (C1-C10) alkane a group, iii) (C6-C40) aryl, further (C6-C30) aryl, each with or without a substituent, or iv) (C3-C40)heteroaryl, further (C3-C30) Aryl groups, each with or without a substituent; wherein R5' is selected from the group consisting of: i) hydrogen or hydrazine, ii) (C1-C20) alkyl, further (C1-C10) alkyl, iii) (C6- C40) aryl, further (C6-C30) aryl, each with or without a substituent, or iv) (C3-C40)heteroaryl, further (C3-C30)heteroaryl, each with or without Substituent, where the L package (C6-C30) an arylene or (C3-C30) heteroaryl group; and wherein if R1' comprises biphenyl, it does not comprise a carbazole; and one or more hydrogens may be selected Sexually replaced by cockroaches; C) Wherein R1" is selected from the group consisting of: i) (C6-C40) aryl, further (C6-C30) aryl, each with or without a substituent, or ii) (C3-C40)heteroaryl, further Is a (C3-C30)heteroaryl group, each with or without a substituent; wherein R2" is selected from the group consisting of: i) hydrogen or hydrazine, ii) (C1-C20) alkyl, further (C1-C10) alkane a group, iii) (C6-C40) aryl, further (C6-C30) aryl, each with or without a substituent, or iv) (C3-C40)heteroaryl, further (C3-C30) Aryl groups, each with or without a substituent; wherein R3" and R4" are independently selected from the group consisting of: i) hydrogen or hydrazine, ii) (C1-C20) alkyl group, further (C1-C10) alkane Base, iii) (C6-C30) aryl, further (C6-C30) aryl, each with or without a substituent, or iv) (C3-C30)heteroaryl, further (C3-C30) Aryl groups, each with or without a substituent; wherein R5" is selected from the group consisting of: i) hydrogen or hydrazine, ii) (C1-C20) alkyl, further (C1-C10) alkyl, iii) (C6- C40) aryl, further (C6-C30) aryl, each with or without a substituent, or iv) (C3-C40)heteroaryl, further (C3-C30)heteroaryl, each with or without Substituent And if the and wherein R1 "comprises biphenyl, then it does not contain carbazole; and wherein one or more hydrogen may be optionally substituted with deuterium; D) of the combination thereof and the like.

Detailed description

As discussed above, the present invention provides a composition comprising at least one compound selected from the group consisting of A, B, C, and D below; each of which is as described above.

The compositions of the present invention may comprise a combination of two or more specific examples described herein.

As used herein, R1 = R ₁ , R2 = R ₂ , etc.; R1' = R _{1 '} , R2' = R _{2 '} , etc.; R1" = R _1" , R2" = R _2" , and many more.

In one embodiment, with respect to Formula 1, R1 is selected from the group consisting of: ii) a (C3-C30)heteroaryl group with or without a substituent; Wherein R2 is selected from the group consisting of: i) a (C6-C30) aryl group with or without a substituent, or ii) a (C3-C30) heteroaryl group with or without a substituent, and wherein R3 is selected from The following: i) hydrogen or deuterium, and wherein formula 1 comprises at least three CN double bonds; and one or more of the hydrogens may be optionally substituted by deuterium; and with respect to formula 2, R1' is selected from the following: i) (C6-C30) aryl with or without a substituent, or ii) (C3-C30)heteroaryl with or without a substituent; wherein R2' is selected from the group consisting of: i) hydrogen or hydrazine, wherein R3 'and R4' are independently selected from the group consisting of: ii) a (C1-C10)alkyl group, wherein R5' is selected from the group consisting of: i) hydrogen or hydrazine, and wherein L comprises (C6-C30) aryl Arylene or (C3-C30) heteroaryl; and wherein if R1' comprises biphenyl, it does not comprise a carbazole; and wherein one or more hydrogens are optionally substituted by deuterium; , R1" is selected from the group consisting of: i) a (C6-C30) aryl group with or without a substituent, or ii) a (C3-C30)heteroaryl group with or without a substituent; wherein R2" is selected from In the following: i) hydrogen or hydrazine wherein R3" and R4" are independently selected from the group consisting of: ii) a (C1-C10)alkyl group, wherein R5" is selected from the group consisting of: i) hydrogen or hydrazine, and wherein R1" contains biphenyl, which does not contain a carbazole; and one or more of the hydrogens may be optionally substituted by deuterium.

In one embodiment, the at least one compound comprises at least one deuterium atom.

In one embodiment, the at least one compound comprises at least three nitrogen atoms.

In one embodiment, the at least one compound has a molecular weight greater than or equal to 450 grams per mole.

In one embodiment, the at least one compound has a molecular weight of from 450 to 800 grams per mole, further from 460 to 700 grams per mole, further from 470 to 600 grams per mole.

In one embodiment, the at least one compound has a molecular weight of from 480 to 600 grams per mole.

In one embodiment, the at least one compound has from -5.30 to - 5.90 eV, further from -5.35 to 5.80 eV, further from -5.40 to - 5.70 eV, and further from a HOMO level of from -5.45 to -5.65 eV.

In one embodiment, the at least one compound has from -1.80 to -2.10 eV, further from -1.87 to -2.10 eV, further from a LUMO level of from -1.85 to -2.10 eV.

In one embodiment, the at least one compound has a λ ^- value of less than or equal to 0.30, further less than or equal to 0.29.

In one embodiment, the at least one compound has a λ ^- value greater than or equal to 0.18, further greater than or equal to 0.20.

In one embodiment, the at least one compound has a glass transition temperature (Tg) of from 105 ° C to 170 ° C, further from 105 ° C to 160 ° C, further from 105 ° C to 150 ° C, and further from 105 ° C to 140 ° C.

In one embodiment, the compound is selected from the group consisting of the following compounds:

In one embodiment, the compound is selected from the group consisting of The group formed is: a, e, h, i, m, n, o, u, v, w, and x.

In one embodiment, the R groups (R1, R2, R3) of Formula 1 are each unsubstituted.

In one embodiment, the R' groups (R1', R2', R3', R4', R5') of the formula 2 are each unsubstituted.

In one embodiment, the R" groups of formula 3 (R1", R2", R3", R4", R5") are each unsubstituted.

In one embodiment, the R groups (R1, R2, R3) of the formula 1 are each an unsubstituted group; the R of the formula 2, a group (R1', R2', R3', R4', R5') Each is an unsubstituted group; and the R" group of the formula 3 (R1", R2", R3", R4", R5") are each an unsubstituted group.

In one embodiment, the compound is selected from the group consisting of: e, h, I, n, u, and x.

In one embodiment, the composition further comprises a metal quinolate.

In one embodiment, the at least one compound is selected from the group consisting of Formula 1.

In one embodiment, with respect to Formula 1, R1 is selected from the following:

In one embodiment, with respect to Formula 1, R2 is selected from the following:

For the above structures and other unspecified structures, the external junction points of each substituent are indicated by wavy lines, as recommended by the current IUPAC standard: Pure Appl . Chem ., 2008 , 80 , 277 (graphical representation of chemical structure diagrams) Graphical representation standards for chemical structural diagrams ).

In one embodiment, with respect to Formula 1, R1 contains greater than or equal to 9 carbon atoms, and further greater than or equal to 12 carbon atoms.

In one embodiment, with respect to Formula 1, R2 comprises greater than or equal to 9 carbon atoms, further greater than or equal to 12 carbon atoms.

The compound of formula 1 may comprise a combination of two or more specific examples as described herein.

In one embodiment, the at least one compound is selected from the group consisting of Formula 2.

In one embodiment, with respect to Formula 2, R1' is selected from the following:

In one embodiment, with respect to Formula 2, L is selected from the group consisting of phenyl or naphthalene. In a further embodiment, with respect to formula 2, L is selected from the group consisting of 1,4-phenylene or 1,4-naphthalene.

In one embodiment, Formula 2, R1' contains greater than or equal to 9 carbon atoms, further greater than or equal to 12 carbon atoms.

In one embodiment, with respect to Formula 2, R2' and R5' are each hydrogen, and R3' and R4' are each a C1-C4 alkyl group, and further each is a methyl group.

The compound of formula 2 may comprise a combination of two or more specific examples as described herein.

In one embodiment, the at least one compound is selected from the group consisting of Formula 3.

In one embodiment, with respect to Formula 3, R1" is selected from the following:

In one embodiment, with respect to Formula 3, R1" contains greater than or equal to 9 carbon atoms, and further greater than or equal to 12 carbon atoms.

In one specific example, with respect to Formula 3, R2" and R5" are each hydrogen, And R3" and R4" are each a C1-C4 alkyl group, and further each is a methyl group.

The compound of formula 3 may comprise a combination of two or more specific examples as described herein.

In one embodiment, the composition comprises from 5 to 100 weight percent, further from 10 to 99 weight percent, and further from 10 to 90 weight percent of formula 1, formula 2, formula 3, based on the weight of the composition. At least one compound or a combination thereof.

In one embodiment, the composition comprises 50 to 90 weight percent of at least one compound of Formula 1, Formula 2, Formula 3, or a combination thereof, based on the weight of the composition. In a further embodiment, the composition comprises from 50 to 80 weight percent of at least one compound of Formula 1, Formula 2, Formula 3, or a combination thereof, based on the weight of the composition.

In one embodiment, the composition further comprises a metal quinolate. In one embodiment, the 8-hydroxyquinoline metal comprises at least one deuterium atom. In a further embodiment, the 8-hydroxyquinoline metal is lithium quinolate.

In one embodiment, the composition further comprises an 8-hydroxyquinoline metal. In one embodiment, the 8-hydroxyquinoline metal is lithium 8-hydroxyquinolate. In a further embodiment, the lithium quinolate contains at least one ruthenium atom.

In one embodiment, the composition comprises from 10 to 90 weight percent of the 8-hydroxyquinoline metal based on the weight of the composition. In a further embodiment, the composition comprises from 10 to 80, further from 10 to 70, further from 10 to 60, based on the weight of the composition, further 10 to 50, by weight of 8-hydroxyquinoline metal. In a further embodiment, the composition comprises from 20 to 50 weight percent of the 8-hydroxyquinoline metal based on the weight of the composition.

In one embodiment, the composition comprises from 10 to 90 weight percent of the 8-hydroxyquinoline metal based on the total weight of the compound of the invention and the 8-hydroxyquinoline metal. In a further embodiment, the composition comprises from 10 to 80, further from 10 to 70, further from 10 to 60, further from 10 to 10, based on the total weight of the compound of the invention and the 8-hydroxyquinoline metal. 50 weight percent of 8-hydroxyquinoline metal. In a further embodiment, the composition comprises from 20 to 50 weight percent of the 8-hydroxyquinoline metal, based on the total weight of the compound of the invention and the 8-hydroxyquinoline metal.

The invention also provides an article comprising at least one component formed from the composition of the invention. In a further embodiment, the article is an organic electroluminescent element.

The present invention provides an article comprising at least one component formed from any of the specific examples described herein, or a combination of two or more specific examples. In one embodiment, the article is an organic electroluminescent device.

The present invention provides a film comprising at least one layer formed from any of the specific examples described herein, or a combination of two or more specific examples.

The present invention provides an electronic component comprising at least one component formed from any one of the specific examples described herein, or a combination of two or more specific examples.

The compositions of the present invention may comprise a combination of two or more specific examples described herein.

The inventive article may comprise a combination of two or more specific examples described herein.

The films of the present invention may comprise a combination of two or more specific examples described herein.

The electronic components of the present invention may comprise a combination of two or more specific examples described herein.

Composition B

An inventive element may comprise a layer formed from the composition of the invention and another layer formed from composition B comprising at least one "HTL compound". The HTL compound is a material that transmits holes at a low driving voltage. High hole mobility is recommended. The HTL is used to assist in blocking the passage of electrons transmitted by the emissive layer. To block electrons typically requires small electron affinity. HTLs are expected to have larger triplets to block the migration of excitons from adjacent EML layers. Examples of HTL compounds include, but are not limited to, bis[(p-tolyl)aminophenyl]-cyclohexane (TPAC); N,N-diphenyl-N,N-bis(3-methylphenyl) -1,1-biphenyl-4,4-diamine (TPD); and N,N'-diphenyl-N,N'-bis(1-naphthyl)-(1,1'-biphenyl )-4,4'-Diamine (NPB).

In one embodiment, the HTL compound is selected from the group consisting of bis[(p-tolyl)amino-phenyl]-cyclohexane (TPAC), N,N-diphenyl-N,N-bis (3- Methylphenyl)-1,1-biphenyl-4,4-diamine (TPD), or N,N'-diphenyl-N,N'-bis(1-naphthyl)-(1,1 '-Biphenyl)-4,4'-diamine (NPB). In a further embodiment, the HTL compound is selected from the group consisting of N,N-diphenyl-N,N-bis(3-methylbenzene) 1,1,1-biphenyl-4,4-diamine (TPD), or N,N'-diphenyl-N,N'-bis(1-naphthyl)-(1,1'-linked Benzene)-4,4'-diamine (NPB). In a further embodiment, the HTL compound is N,N'-diphenyl-N,N'-bis(1-naphthyl)-(1,1'-biphenyl)-4,4'-diamine. (NPB).

Preferably, composition B comprises 100 weight percent of the HTL compound based on the weight of composition B.

Composition B can comprise a combination of two or more specific examples as described herein. Layer B formed by composition B may comprise a combination of two or more specific examples as described herein.

definition

The term "aryl" as used herein refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom therefrom. The aryl group may be a monocyclic and/or fused ring system, each ring suitably containing from 4 to 7 atoms, preferably 5 or 6 atoms. Also included are structures in which two or more aryl groups are combined via a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, binaphthyl (eg, 1,1 '-binaphthyl), biphenyl, anthracenyl, fluorenyl, fluorenyl (eg, 9,9-( Dimethyl-2-indenyl)), phenylfluorenyl (for example, 4-(9,9-dimethyl-2-indenyl)phenyl), benzofluorenyl, phenanthryl, orthotriphenyl (triphenylenyl), fluorenyl, perylenyl, fluorenyl, naphchacenyl, fluoranthenyl, decylnaphthyl (eg, 9,9-(dimethyl-) 2-indenyl)naphthyl) and the like, but is not limited thereto. The naphthyl group may be 1-naphthyl or 2-naphthyl, and the fluorenyl group may be 1-indenyl, 2-indenyl or 9-fluorenyl, and the fluorenyl group may be 1-indenyl or 2-indenyl. Any of 3-mercapto, 4-indenyl and 9-fluorenyl.

The term "heteroaryl" as used herein denotes an aryl group containing at least one hetero atom; examples for an aromatic cyclic main chain are B, N, O, S, P(=O), Si and P, and examples for the remaining aromatic cyclic backbone atoms are carbon atoms. The heteroaryl group can be a 5- or 6-membered monocyclic heteroaryl or polycyclic heteroaryl which can be fused to one or more benzene rings and can be partially saturated. Also included are structures having one or more heteroaryl groups bonded via a single bond. Also included are structures having an aryl or heteroaryl group bonded via a single bond. The heteroaryl group may include a divalent aryl group whose hetero atom is oxidized or quaternized to form an N-oxide, a quaternary salt, or the like. Specific examples include, but are not limited to, monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, iso Azolyl, Azolyl, Diazolyl, three Base, four Base, triazolyl, tetrazolyl, furazolyl, pyridyl, pyridyl Base, pyrimidinyl, oxime Polycyclic heteroaryl group, such as benzofuranyl, dibenzofuranyl, fluoreno[4,3-b]benzofuranyl, benzothiophene Base, dibenzothiophenyl, sterol [4,3-b]benzothiophenyl, isobenzofuranyl, benzimidazolyl, phenylbenzoimidazolyl (eg, 2-phenyl-) 1-benzimidazolyl), benzothiazolyl (for example, 1-benzothiazolyl), phenylbenzothiazolyl (for example, 4-(1-benzothiazolyl)phenyl), benzo Azolyl (eg, 1-benzo) Azoyl), phenylbenzo Azolyl (for example) 4-(1-benzo) Azyl)phenyl), benzisothiazolyl, benziso Azolyl, benzo Azyl, isodecyl, decyl, oxazolyl, benzothiadiazolyl, quinolyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, anthracene Azolyl (eg, 9-carbazolyl), phenyloxazolyl (eg, 9-phenyl-3-oxazolyl), morphinyl, quinolinylphenyl (eg, 4-(8-quinoline) Phenyl)phenyl), dibenzofuranylphenyl (for example, 4-(4-dibenzofuranyl)phenyl), and benzodioxolyl; and their corresponding N-oxidation (eg, pyridyl N-oxide, quinolinyl N-oxide) and its quaternary salts.

Substituents include, but are not limited to, the following: hydrazine, halogen, (C1-C30)alkyl with or without a halogen substituent, (C6-C30) aryl, with or without (C6-C30) aryl substituent ( a C3-C30)heteroaryl group, a 5- to 7-membered heterocycloalkyl group selected from one or more heteroatoms selected from, for example, B, N, O, S, P(=O), Si, and P, fused 5 to 7 membered heterocycloalkyl of one or more aromatic rings, (C3-C30)cycloalkyl, (C5-C30)cycloalkyl fused to one or more aromatic rings, tri(C1-C30) alkane Base alkyl, di(C1-C30)alkyl (C6-C30) arylalkyl, tris(C6-C30)aryldecyl, adamantyl, (C7-C30)bicycloalkyl, (C2-C30 Alkenyl, (C2-C30)alkynyl, cyano, oxazolyl, NR ₂ iR ₂₂ , BR ₂₃ R ₂₄ , PR ₂₅ R ₂₆ , P(=O)R ₂₇ R ₂₈ [wherein R ₂ i to R ₂₈ independently represents (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl], (C6-C30)aryl(C1-C30)alkyl, (C1-C30)alkyl (C6-C30) aryl, (C1-C30)alkyloxy, (C1-C30)alkylthio, (C6-C30)aryloxy, (C6-C30)arylthio, (C1 -C30) alkoxycarbonyl, (C1-C30)alkylcarbonyl, (C6-C30)arylcarbonyl, (C6-C30)aryloxycarbonyl, (C1-C30)alkoxy Alkylcarbonyloxy, (C1-C30)alkylcarbonyloxy, (C6-C30)arylcarbonyloxy, (C6-C30)aryloxycarbonyloxy, carboxy, nitro and hydroxy; or adjacent The substituents are linked together to form a ring. For example, a substituent may form a cyclic structure with one or more atoms on a backbone molecule comprising the substituent.

experiment

Reagents and test methods

All solvents and reagents were obtained from suppliers including Sigma-Aldrich, Fisher Scientific, Acros, TCI, and Alfa Aesar. It can be used in the highest available purity and/or can be recrystallized before use if needed. Dry solvents were obtained from a laboratory purification/distribution system (hexane, toluene, tetrahydrofuran, and diethyl ether) or purchased from Sigma. All experiments involving water sensitive com-pounds were performed in "oven-dried" glassware under a nitrogen atmosphere or in a glove box. The reaction was monitored by analytical thin layer chromatography (TLC) on a pre-coated aluminum plate (VWR 60 F254) and visualized by ultraviolet light and/or potassium permanganate staining. Rapid Tomography was performed on a ISCO COMBIFLASH system using a GRACESOLV cartridge.

Unless otherwise noted, 1H-NMR spectra (500 MHz or 400 MHz) were obtained from a Varian VNMRS-500 or VNMRS-400 spectrometer at 30 °C. The chemical shift depends on the NMR solvent used. Refer to the following: TMS ( δ = 0.00) in CDCl ₃ , benzene - d ₅ (7.15) in benzene- d ₆ or DMSO- d ₅ in DMSO- d ₆ ( δ 2.50). If necessary, peak assignment is performed with the help of COSY, HSQC, or NOESY experiments to determine the structural body.

¹³ C-NMR spectra (125 MHz or 100 MHz) were obtained from a Villian VNMRS-500 or VNMRS-400 spectrometer, and depending on the NMR solvent used, reference may be made to the solvent or standard signal (0.0-TMS to CDCl ₃ , 128.02) - Benzene- d ₆ , 39.43-DMSO- d ₆ ).

A routine LC/MS study was performed as follows. A 5 μl sample, such as "3 mg/ml in THF", is injected into an AGILENT 1200SL binary gradient liquid chromatography coupled to the Aegean 6520 QTof, a quadrupole time-of-flight mass spectrometer system. Performed through a dual spray electric spray (ESI) interface operating in PI mode. The following analytical conditions were used: column: 150 x 4.6 mm ID, 3.5 micron bus (ZORBAX) SB-C8; column temperature: 40 ° C; mobile phase: 75/25 A/B to 15/85 A/B at 40 Minute; solvent A = 0.1 v% formic acid in water; solvent B = THF; flow rate 1.0 ml / min; UV detection: diode array 210 to 600 nm (extraction wavelength 250 nm, 280 nm); ESI Conditions: gas temperature 365 ° C; gas flow rate - 8 ml / min; capillary 3.5 kV; atomizer 40 PSI; segmenter (fragmentor) 145V.

All cycles of DSC measurements were made on a TA Instruments Q2000 instrument at a scan rate of 10 ° C/min and under a nitrogen atmosphere. The sample was scanned from room temperature to 300 ° C, cooled to -60 ° C, and heated again to 300 ° C. The glass transition temperature (Tg) is measured in the second heating scan. Data analysis was performed using Texas Instruments Universal Analysis software. The Tg is calculated using the "onset-at-inflection" method.

All calculated system using Gaussian 09 (Gaussian09) Program ^1. The calculation is performed using the Mixed Density Function Theory (DFT) method, B3LYP ^2, and 6-31G*(5d) basic set ³ (basis set. ³ ). Singlet calculations use closed shell approximation, and triplet calculations use open shell approximation. All values are quoted in electron volts (eV). The HOMO value and the LUMO value are determined from the orbital energy of the best geometry of the singlet ground state. The difference between the total energy of the best triplet state and the total energy of the best singlet state is determined as the triplet energy.

1. Gaussian 09, Revision A.02, Frisch, MJ et al; Gaussian, Inc., Wallingford CT, 2009. 2. (a) Becke, AD J. Chem. Phys. 1993 , 98, 5648. (b) Lee, C.; Yang, W.; Parr, RG Phys. Rev B 1988 , 37, 785. (c) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett. 1989 , 157, 200. 3. (a) Ditchfield, R.; Hehre, WJ; Pople, JA J. Chem. Phys. 1971 , 54, 724. (b) Hehre, WJ; Ditchfield, R.; Pople, JA J. Chem. Phys. 1972 , 56, 2257. (c) Gordon, MS Chem. Phys. Lett. 1980 , 76, 163.

The procedure described in the reference ( J. Phys . Chem . A, 2003, 107, 5241-5251) was applied to calculate the recombination energy (λ ^- ) of each molecule, which is an indicator of electron mobility.

Individual reaction

4-bromo-N-(2-(anilino)phenyl)benzamide (precursor 1)

A four neck, 2 L round bottom flask was fitted with a thermocouple, a 500 mL addition funnel, a nitrogen needle inlet, and an overhead stirrer. 4-Bromobenzylidene chloride (23.8 g, 108.4 mmol) and N,N -dimethylacetamide (DMAC, 125 mL) were added to the flask. A solution of N -phenyl-o-phenylenediamine in DMAC (300 mL) was added dropwise over a 40 min portion over EtOAc (20.0 g, 108.6 mmol). Once the addition was complete, the reaction was stirred at room temperature for 1 h. The addition of 1.1 L of deionized water to the flask with vigorous agitation resulted in the formation of a precipitate. The mixture was stirred at room temperature for 1 h, and then filtered by a course porosity fritted filter to separate the solid. The solid was washed with hexanes (3×200 mL) and EtOAc (EtOAc)

^{1 H NMR (400MHz, DMSO- d} 6) δ 9.77 (sM, 1H), 7.84 (d, J = 8.6Hz, 2H), 7.70 (d, J = 8.6Hz, 2H), 7.54 (dd, J = 7.9 , 1.2 Hz, 1H), 7.47 (s, 1H), 7.30 (dd, J = 8.1, 1.3 Hz, 1H), 7.23-7.10 (m, 3H), 7.00 (td, J = 7.8, 1.4 Hz, 1H) , 6.92 (dd, J = 8.6, 1.0 Hz, 2H), 6.79 (t, J = 7.3 Hz, 1H). ¹³ C NMR (101 MHz, DMSO- d ₆ ) δ 164.68, 143.88, 137.06, 133.67, 131.24, 129.80, 129.02, 128.74, 126.53, 126.10, 125.20, 121.36, 119.69, 119.53, 116.61.

2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazole (precursor 2)

A four-neck 1L round bottom flask equipped with an overhead stirrer, thermocouple, heating pack, and water condenser plus nitrogen inlet, charged with 4-bromo-N-(2-(anilino)phenyl)benzonitrile Amine (9.0 g, 24.51 mmol) and glacial acetic acid (350 mL). The reaction was heated to an internal temperature of 115 ° C during 30 min, at which time the solid was completely dissolved and the reaction was completed as indicated by HPLC analysis. The reaction was allowed to cool to room temperature and the acetic acid was removed via rotary evaporation to afford a pink solid. The solid residue was dissolved in the CH ₂ Cl _2, concentrated and silica gel (~ 60g) on. The silica gel mixture is then loaded and silica gel plug (silica gel plug) (~ 0.5 " high, chert 30g), and be eluted with _{CH 2 Cl 2 (~ 5L)} . Via rotary evaporation to remove The solvent was obtained to give 32.7 g (yield: EtOAc, EtOAc)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.91-7.85 (m, 1H), 7.56-7.46 (m, 3H), 7.43 (s, 4H), 7.37-7.20 (m, 5H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 151.23, 142.94, 137.28, 136.78, 131.57, 130.86, 130.02, 128.94, 128.79, 127.38, 124.06, 123.60, 123.17, 119.93, 110.50.

1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-di) Pentaborane-2-yl)phenyl)-1H-benzo[d]imidazole (1-Phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2) -yl)phenyl)-1H-benzo[d]imidazole ) (precursor 3)

A four-neck, 500 mL round bottom flask equipped with an overhead stirrer, nitrogen inlet, 125 mL addition funnel, and thermocouple was rinsed with dry nitrogen for 10 minutes. The flask was charged with 2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazole (25.0 g, 71.59 mmol) and THF (250 mL), and the reaction was cooled to an internal temperature of -71 °C. 1.6 M n-butyllithium (67 mL, 107.2 mmol) in hexane was added dropwise via an addition funnel over 30 minutes, and stirred at an internal temperature of -72 ° C for an additional 30 minutes. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-di was added dropwise via an addition funnel Dioxaborolane (32 mL, 171.99 mmol) was taken to a deep red solution for 30 minutes maintaining the temperature below -70 °C. The cold bath was removed and the yellow slurry was allowed to warm to room temperature and stirred for 16 h. The reaction was concentrated via rotary evaporation, then taken up in dichloromethane (350 mL) and washed with water (200mL) The organic layer with dichloromethane (2 x 150mL) and the aqueous layer was extracted, and the combined and dried over MgSO _4, filtered, and concentrated via rotary evaporation. The resulting yellow solid was washed with hexanes (100 mL) which removed most of the color to afford 22.2 g of light brown solid. The solid was separated into two portions and recrystallized from EtOAc (EtOAc: EtOAc: EtOAc: EtOAc:

(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)boronic acid ( precursor 4)

The oven-dried round bottom flask was charged with 2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazole, (21.7 g, 62.3 mmol), anhydrous tetrahydrofuran (110 mL) and TEFLON. Stir the stick. The solution was quenched to -78 °C then 1.6 M n-BuLi (46.7 mL, 74.7 mmol) with hexanes was then added over 30 mins. This dark solution was stirred at -78 °C for 30 min then B (OMe) ₃ (21.2 mL, 187 mmol) was then added over 30 min. The reaction mixture was allowed to stir and warmed to RT overnight. 75 mL of 2.5 N HCl (aq) and 75 mL of deionized water were added to the THF solution. This mixture was stirred at RT for 5 h. The acidic solution was neutralized by adding Na ₂ CO ₃ in portions over a period of 10 minutes. Once the solvent was removed via rotary evaporation, the residue was subjected to soxhlet extraction for 2 h, but the color of the solid was not removed. The resulting solid was stirred in warm toluene (50 ° C) for 1 hr. The toluene slurry was filtered on a sintered filter and the solid was washed with fresh hexane. Excess hexane was added to the toluene solution, resulting in solid precipitation. This solid was collected by filtration and washed with fresh hexane. The product was dried with EtOAc (EtOAc:EtOAc)

¹ H NMR (400 MHz, DMSO- d ₆ ) δ 8.14 (W, 1H), 7.87-7.78 (m, 1H), 7.78-7.73 (m, 1H), 7.65-7.46 (m, 4H), 7.47-7.38 (m, 2H), 7.30 (dtd, J = 15.0, 7.2, 1.3 Hz, 2H), 7.20 (dd, J = 7.2, 0.8 Hz, 1H). ¹³ C NMR (101 MHz, DMSO- d ₆ ) δ 151.83, 142.22, 136.96, 136.36, 133.85, 130.89, 129.98, 128.82, 128.05, 127.47, 123.44, 122.83, 119.23, 110.48.

2-Chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)quinazoline (2-Chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)quinazoline ) (precursor 5)

A three-neck, 500 mL round bottom flask was fitted with a heating pack, a water condenser, a nitrogen inlet, and a stir bar. Add 9,9-dimethylfluorene-2-boronic acid pinacol ester (5.08 g, 15.86 mmol), 2,4-dichloroquinazoline (3.79 g) , 19.04 mmol), potassium carbonate (6.90 g, 49.9 mmol, 3.2 eq), triphenylphosphine (0.208 g, 0.79 mmol), and palladium acetate (0.070 g, 0.31 mmol) to the flask, and the flask was rinsed with nitrogen for 10 min. . Deionized water (50 mL), acetonitrile (50 mL), and toluene (250 mL) were added to a "1L graduated cylinder" and the solvent mixture was sprayed with nitrogen for 10 minutes and then added to the reaction flask. The pale yellow reaction mixture was stirred for 21 h under reflux conditions (internal temperature of 76 ° C). The reaction was allowed to cool to 45 ° C then transferred to a 500 mL sep. funnel washed with toluene (50 mL). The layers were separated and the aqueous layer was extracted with dichloromethane (50 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated with EtOAc EtOAc. The solid was dissolved in hot toluene (~100 mL) and then cooled to 0 ° C to form a precipitate. The yellow solid was isolated and the filtrate was concentrated by rotary evaporation and tribr. The title compound (4.74 g, 13.3 mmol, 84%)

_{^{1 H NMR (400MHz, CDCl 3}} ) δ 8.20 (ddd, J = 8.4,1.3,0.6Hz, 1H), 8.09-8.03 (m, 1H), 7.98-7.85 (m, 3H), 7.85-7.80 (m, 1H), 7.78 (dd, J = 7.8, 1.6 Hz, 1H), 7.64 (ddd, J = 8.3, 6.9, 1.2 Hz, 1H), 7.49 (ddd, J = 7.5, 3.7, 2.3 Hz, 1H), 7.44 -7.36 (m, 2H), 1.57 (s, 6H). ¹³ C NMR (101MHz, CDCl ₃ ) δ 172.01, 157.11, 154.33, 154.11, 153.13, 141.93, 138.08, 134.74, 134.62, 129.65, 128.33, 128.13, 127.91, 127.63, 127.27, 124.64, 122.81, 121.78, 120.74, 120.10, 47.22, 27.12.

9-(2-chloroquinazolin-4-yl)-9H-carbazole (9-(2-Chloroquinazolin-4-yl)-9H-carbazole ) (precursor 6 )

In a nitrogen-washed glove box, two oven-dried 200-mL jars were each filled with 80 mL of anhydrous THF (pre-cooled to -25 ° C, plus aluminum block). Add carbazole (5 g, 29.9 mmol) to a jar followed by slow addition of solid KH (1.32 g, 32.9 mmol) to afford anion. In a separate jar, 2,4-dichloroquinazoline (5.95 g, 29.9 mmol) was dissolved in THF. The carbazole anion solution was slowly added to the quinazoline solution using a syringe. Allow the dark solution to warm to room temperature. After 1 h, GC-MS showed complete conversion to the desired product. The solution was removed from the glove box and water (2 mL) was carefully added to quench any remaining KH. The solution was poured into water (200 mL) and a yellow solid formed. This solid was collected by filtration and washed with water. The solid was dissolved in methylene chloride (200 mL), and the solution was dried over MgSO ₄ and filtered. Hexane (~100 mL) was added until the solution became cloudy. Methylene chloride was added until the solution became clear and the solution was placed in a freezer. After 1 h, pale yellow crystals formed. The solution was stored in the freezer for 72 h. The crystals were collected by filtration and dried under vacuum to yield 3.65 g of product as pale yellow needles. The solvent was removed from the filtrate and recrystallized from methylene chloride / hexanes (100mL / 150mL) to yield another crop of fresh yellow crystals (3.6 g) (7.2 g, 73%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.17-8.11 (m, 3H), 8.02 - 7.94 (m, 1H), 7.89 (ddd, J = 8.5, 1.4, 0.7 Hz, 1H), 7.58-7.49 (m, 1H), 7.48-7.34 (m, 6H).

¹³ C NMR (101 MHz, CDCl ₃ ) δ 159.97, 156.72, 154.65, 139.99, 135.65, 128.31, 127.75, 126.48, 126.33, 125.11, 122.27, 120.33, 118.57, 112.07.

2-chloro-4-(naphthalen-1-yl)quinazoline (precursor 7)

In a glove box, Pd(PPh ₃ ) ₄ (2.2 gg, 1.9 mmol, 5 mol%) was charged with magnetically stirred 2,4-dichloroquinazoline (7.5 g, 38 mmol), 1-naphthylboronic acid (1-naphthylboronic) Acid) (6.5 g, 38 mmol, 1 eq.), and a mixture of powder CsF (11.5 g, 76 mmol, 2 eq.) in 150 mL dry toluene. The reaction mixture was heated at 100 ° C overnight. The solvent was removed, and the crude product was dissolved in chloroform, washed with water, and the organic layer was concentrated to a small volume, which was loaded into a small hydrazine gel plug to remove color and residual borate. The product was dry-loaded in an ISCO purification system and eluted with chloroform/hexane gradient to afford 9 g (31 mmol, 81%) of desired compound.

_{^{1 H NMR (500MHz, CDCl 3}} ) δ 8.14-8.08 (m, 1H), 8.05 (t, J = 9.2Hz, 1H), 8.00-7.90 (m, 2H), 7.69-7.58 (m, 3H), 7.57 -7.45 (m, 3H), 7.45-7.38 (m, 1H). ¹³ C NMR (126MHz, CDCl ₃ ) δ 172.37, 157.10, 152.56, 135.25, 133.58, 133.11, 131.25, 130.46, 128.49, 128.13, 128.03, 127.96, 127.73, 127.11, 126.47, 125.24, 124.99, 123.30

8-(4-bromophenyl)quinoline (precursor 8)

Quinoline-4-boronic acid (15.16 g, 87.64 mmol), 1-iodo-4-bromobenzene (27.03 g, 95.55 mmol), palladium acetate (0.388 g, 1.73 mmol), and triphenylphosphine (1.14 g, 4.35 mmol) was charged with a 1 L round bottom flask equipped with a stir bar, a heating pack, a thermocouple, and a water condenser with a nitrogen inlet. The flask was flushed with nitrogen for 5 minutes, then degassed with toluene (360 mL), ethanol (120 mL), and diluted with water to 120 mL, 40 wt% potassium phosphate tribasic (115.5 g, 217.65 mmol). And added to the reaction. The reaction was heated to an internal temperature (reflux) of 74 ° C and stirred for 15 h. The reaction was allowed to cool to room temperature and the layers were separated. With ethyl acetate (2 x 250 mL) The aqueous layer was extracted, and the combined organic layers were dried over magnesium sulfate, filtered, and concentrated by rotary evaporation. The material was purified by EtOAc (EtOAc/EtOAc)

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.94 (dd, J = 4.2, 1.8 Hz, 1H), 8.20 (dd, J = 8.3, 1.8 Hz, 1H), 7.84 (dd, J = 8.1, 1.5 Hz, 1H) ), 7.70 (dd, J = 7.1, 1.5 Hz, 1H), 7.64 - 7.54 (m, 5H), 7.42 (dd, J = 8.3, 4.2 Hz, 1H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 150.36, 145.81, 139.65, 138.41, 136.31, 132.26, 131.14, 130.09, 128.77, 127.93, 126.28, 121.79, 121.16.

8-(4-(4,4,5,5-tetramethyl-1,3,2-di) Pentaborane-2-yl)phenyl)quinoline (precursor 9)

A 1 L, three-necked round bottom flask equipped with an overhead stirrer, heating pack, thermocouple, and water condenser plus nitrogen inlet, charged with precursor 8 (19.99 g, 70.35 mmol), bis (charinol) Boric acid ester (bis(pinacolato)diboron) (21.47 g, 84.55 mmol), potassium acetate (13.90 g, 143.63 mmol), and bis(triphenylphosphine)palladium(II) chloride (2.47 g, 3.52 mmol) And rinse the flask with nitrogen for 5 minutes. Then degas the already blown nitrogen through the 1,4-two for 5 minutes. Alkane (350 mL) was added to the flask and the reaction was heated to 100 °C. The reaction was stirred at this temperature for 3 h and then allowed to cool to room temperature. Brine (250 mL) was added followed by ethyl acetate (500 mL). The aqueous layer was extracted with EtOAc (EtOAc) (EtOAc)EtOAc. The material was dissolved in dichloromethane and concentrated on approximately 45 g of hydrazine gel and purified by normal phase flash chromatography (methylene chloride / ethyl acetate) to provide an oily residue. . The material was triturated with pentane (50 mL) and filtered to afford product (22.42 g, 67.69 mmol, 96%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.94 (dd, J = 4.2, 1.8 Hz, 1H), 8.19 (dd, J = 8.3, 1.8 Hz, 1H), 7.99-7.89 (m, 2H), 7.83 (dd , J = 8.1, 1.5 Hz, 1H), 7.76-7.66 (m, 3H), 7.60 (dd, J = 8.1, 7.2 Hz, 1H), 7.40 (dd, J = 8.3, 4.2 Hz, 1H), 1.37 ( s, 12H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 150.30, 142.52, 140.92, 136.13, 134.42, 130.18, 129.96, 128.69, 127.68, 126.21, 121.01, 83.71, 25.03, 24.86.

2-Chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)quinazoline (2-Chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)quinazoline ) (precursor 10)

A three-neck, 500 mL round bottom flask was fitted with a heating pack, a water condenser, a nitrogen inlet, and a stir bar. Add 9,9-dimethylfluorene-2-boronic acid pinacol Ester) (5.08 g, 15.86 mmol), 2,4-dichloroquinazoline (3.79 g, 19.04 mmol), potassium carbonate (6.90 g, 49.9 mmol, 3.2 eq), triphenylphosphine (0.208 g, 0.79 mmol) , and palladium acetate (0.070 g, 0.31 mmol) to the flask, and the flask was rinsed with nitrogen for 10 minutes. Deionized water (50 mL), acetonitrile (50 mL), and toluene (250 mL) were added to a "1L graduated cylinder" and the solvent mixture was sprayed with nitrogen for 10 minutes and then added to the reaction flask. The pale yellow reaction mixture was stirred for 21 h under reflux conditions (internal temperature of 76 ° C). The reaction was allowed to cool to 45 ° C then transferred to a toluene (50 mL) washed 500 mL sep. funnel. The layers were separated and the aqueous layer was extracted with dichloromethane (50 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated with EtOAc EtOAc. The solid was dissolved in hot toluene (~100 mL) and then cooled to 0 ° C to form a precipitate. The yellow solid was isolated and the filtrate was concentrated by rotary evaporation and triturated with 25 mL of toluene. The title compound (4.74 g, 13.3 mmol, 84%)

_{^{1 H NMR (400MHz, CDCl 3}} ) δ 8.20 (ddd, J = 8.4,1.3,0.6Hz, 1H), 8.09-8.03 (m, 1H), 7.98-7.85 (m, 3H), 7.85-7.80 (m, 1H), 7.78 (dd, J = 7.8, 1.6 Hz, 1H), 7.64 (ddd, J = 8.3, 6.9, 1.2 Hz, 1H), 7.49 (ddd, J = 7.5, 3.7, 2.3 Hz, 1H), 7.44 -7.36 (m, 2H), 1.57 (s, 6H). ¹³ C NMR (101MHz, CDCl ₃ ) δ 172.01, 157.11, 154.33, 154.11, 153.13, 141.93, 138.08, 134.74, 134.62, 129.65, 128.33, 128.13, 127.91, 127.63, 127.27, 124.64, 122.81, 121.78, 120.74, 120.10, 47.22, 27.12.

9-(2-(4-(1-phenyl-1H-indol-2-yl)phenyl)quinazolin-4-yl)-9H-carbazole (9-(2-(4-(1) -Phenyl-1H-indol-2-yl)phenyl)quinazolin-4-yl)-9H-carbazole) (Compound 1)

Weighed 2-chloroquina-zoline-4-carbazolylquinazoline (5 g, 14.9 mmol), phenyl benzimidazol-phenyl Boronic acid) (6.6 g, 16.3 mmol), palladium acetate (0.1 g, 0.45 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxyhexinophosphino-2', 6'-dimethoxybiphenyl) (sPhos, available from Aldrich) (0.37 g, 0.89 mmol, available from Aldrich), and potassium phosphate (5.3 g, 29.7 mmol) to an oven-dried, 1 L, 3-neck round Inside the bottom flask. A stir bar was added and nitrogen sprayed toluene (250 mL) was added. The reaction mixture was stirred at 100 ° C for 10 minutes, then degassed deionized water (50 mL) was added, and the reaction was stirred for 4 hours, after which the fractional LC-MS analysis showed approximately 30% conversion. More toluene (200 mL) and water (100 mL) were added, and the reaction was stirred at 100 ° C overnight. Thereafter, LC-MS analysis of the fractions of the reaction mixture showed that the starting material was completely converted to the desired product, which was diluted with dichloromethane (DCM) (300 mL) and quenched with water (100 mL).

The aqueous fraction was washed with more DCM (2 x 150 mL) and the organic fractions were combined, dried over sodium sulfate and solvent was evaporated in vacuo. The residue was purified by column chromatography on an ISCO system using EtOAc/hexane solvent system, and purified product (7.5 g, 94% yield, and 98% purity according to LC) at 55 ° C , dissolved in DCM (~200mL). The hexane solvent was slowly added, and the solution was placed in a refrigerator to crystallize the product. The fine crystals were filtered under suction using a sintered tightly equipped Buchner funnel and dried to provide 7 g (93% recovery) of the desired product. A second ISCO column chromatography and recrystallization from hot DCM/acetonitrile afforded a final product of 99.4% purity according to LC-MS.

_{^{1 H NMR (500MHz, CDCl 3}} ) δ 8.66-8.59 (m, 2H), 8.24 (d, J = 8.2Hz, 1H), 8.22-8.16 (m, 2H), 8.00-7.91 (m, 2H), 7.85 (dd, J = 8.4, 0.7 Hz, 1H), 7.80-7.73 (m, 2H), 7.56-7.44 (m, 6H), 7.45-7.34 (m, 7H), 7.34-7.26 (m, 3H).

¹³ C NMR (126 MHz, CDCl ₃ ) δ 160.10,158.28,153.96,151.92,143.13,140.44,138.27,137.40,137.00,134.60,132.23,129.94,129.74,129.37,128.66,128.51,127.43,127.29,126.26,125.94, 124.79, 123.53, 123.08, 121.58, 120.33, 119.99, 119.01, 111.98, 110.48.

4-(naphthalen-1-yl)-2-(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)quinazoline ( Compound 2 )

In a glove box, Pd(dppf)Cl ₂ (0.3 g, 0.36 mmol, 3 mol%) was charged with magnetically stirred 2-naphthalene-4-chloroquinazoline (3.5 g, 12 mmol), 1-phenyl-2-( 4-(4,4,5,5-tetramethyl-1,3,2s-two Penrolor-2-yl)phenyl)-1H-benzo[d]imidazole (4.8 g, 12 mmol, 3 equivalents), and in combination with 100 mL of A mixture of the powder of the alkane KOAc (2.94 g, 30 mmol, 2.5 eq.). The reaction mixture was heated at 80 ° C overnight. Water was added to the solid and the organics were extracted into chloroform. The organic layer was dried, the solvent was removed, and the product was purified by flash chromatography (ISCO EtOAc), using chloroform/EtOAc gradient to give the desired compound (~5.5 g, 87% yield, according to LC It is ~99% pure). The product was recrystallized from boiling chlorobenzene to afford the desired product (4.5 g, >99.8% pure LC).

_{^{1 H NMR (500MHz, CDCl 3}} ) δ 8.68-8.61 (m, 2H), 8.19 (ddd, J = 8.5,1.1,0.7Hz, 1H), 8.10-8.04 (m, 1H), 8.01-7.97 (m, 1H), 7.95-7.87 (m, 2H), 7.77-7.71 (m, 2H), 7.69-7.58 (m, 4H), 7.57-7.33 (m, 9H), 7.33-7.28 (m, 1H), 7.27- 7.23 (m, 1H)

¹³ C NMR (126MHz, CDCl ₃ ) δ 168.99, 159.58, 151.99, 151.38, 143.00, 138.89, 137.29, 136.93, 134.70, 133.90, 133.61, 131.69, 131.51, 129.84, 129.71, 129.56, 128.94, 128.54, 128.33, 127.81, 127.37, 127.23, 127.19, 126.64, 126.17, 125.60, 124.98, 123.39, 123.36, 122.97, 119.84, 110.39.

9-(2-(9,9-Dimethyl-9H-indol-2-yl)quinazolin-4-yl)-9H-indazole (Compound 3)

In a 500-mL, 3-neck RB flask equipped with a reflux condenser, 9-(2-chloro-quinazolin-4-yl)-9H-carbazole (4.00 g, 12.13 mmol), 2-( ,9,-ditetramethyl-9H-indol-2-yl)-4,4,5,5-tetramethyl-1,3,2-di Penrolane (4.27 g, 13.34 mmol), palladium acetate (0.054 g, 0.24 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (s-phos) (0.30 g) 0.73 mmol, available from Aldrich), and potassium phosphate (6.04 g, 36.39 mmol) in combination with 100 mL of sprayed toluene. Sprayed water (20 mL) was added and the mixture was heated to 100 °C for 1 hr. Component TLC analysis showed no conversion to product. Tetrakistriphenylphosphine palladium (12 mg, 0.01 mmol) was added, and the mixture was heated at 100 ° C for 1 hr. TLC showed conversion to a new product, along with the remaining starting material. The mixture was heated at 100 ° C overnight. TLC and LC-MS showed the presence of the desired product as well as a small amount of chlorine starting material and excess boronic acid ester. The reaction mixture was allowed to cool to 60 ° C and transferred to a sep. funnel. The organic layer was loaded onto a gel plug and eluted with methylene chloride. The solvent was removed to yield 6 g of a crude material as a yellow solid. The material was further purified using an ISCO automated chromatography unit using a gradient of hexane/methylene chloride (10-100% methylene chloride). The title compound (3 g, 51%) was obtained as a solid.

_{^{1 H NMR (400MHz, cdcl 3}} ) δ 8.78-8.74 (m, 1H), 8.69 (dd, J = 8.0,1.6Hz, 1H), 8.30-8.22 (m, 1H), 8.21-8.14 (m, 2H) , 7.91 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H), 7.88-7.73 (m, 3H), 7.57-7.30 (m, 10H), 1.58 (s, 6H).

¹³ C NMR (101 MHz, cdcl ₃ ) δ 161.16, 158.08, 154.66, 154.14, 154.12, 142.15, 140.55, 138.66, 136.61, 134.46, 129.33, 128.19, 127.89, 127.10, 126.87, 126.26, 125.94, 124.77, 122.86, 122.74, 121.54, 120.62, 120.35, 120.19, 118.83, 112.16, 47.08, 27.20.

4-(9,9-Dimethyl-9H-indol-2-yl)-2-(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)quinazoline (Compound 4)

A 500 mL, three-necked round bottom flask equipped with a stir bar, a heating pack, and a water condenser plus a nitrogen inlet was charged with 2-chloro-4-(9,9-dimethyl-9H-indol-2-yl) Quinazoline (3.19 g, 8.9 mmol), 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-di) Penrolbor-2-yl)phenyl)-1H-benzo[d]imidazole (3.50 g, 8.8 mmol), and potassium phosphate tribasic monohydrate (7.23 g, 31.4 mmol), and nitrogen Rinse for 10 minutes. Add 1,4-two Alkane to the flask (150 mL). A stock solution of palladium was prepared in separate 100 mL round bottom flasks. Add palladium acetate (0.041 g, 0.18 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) (0.337 g, 0.70 mmol, available from Aldrich ) to the flask and rinse the contents of the flask with nitrogen. Then add 25mL of 1,4-two The alkane was stirred for 5 minutes and then added to a 500 mL reaction flask. 44 mL of water (degassed with nitrogen) was then added to the reaction and the reaction was heated to an internal temperature of 75 °C for 17 h. The reaction was allowed to cool to room temperature then partitioned between water (100 mL) and dichloromethane (EtOAc) (EtOAc) Concentrated by rotary evaporation. The brown solid was dissolved in acetone and concentrated on a 25 g hydrazine gel and purified by normal phase flash chromatography (0 to 100% ethyl acetate / hexane). The title compound (2.95 g, 4.99 mmol, 57%) was obtained as a white solid.

_{^{1 H NMR (400MHz, CDCl 3}} ) δ 8.68 (d, J = 8.7Hz, 2H), 8.23-8.11 (m, 2H), 7.96-7.89 (m, 4H), 7.89-7.80 (m, 2H), 7.76 (d, J = 8.7 Hz, 2H), 7.58 (ddd, J = 8.2, 6.9, 1.2 Hz, 1H), 7.55-7.45 (m, 4H), 7.43 - 7.33 (m, 5H), 7.32 - 7.26 (m , 2H), 1.59 (s, 6H).

¹³ C NMR (101 MHz, CDCl ₃ ) δ 168.77, 159.48, 154.26, 153.88, 152.18, 152.03, 143.14, 141.22, 139.07, 138.38, 137.37, 137.06, 136.30, 133.63, 131.77, 129.94, 129.67, 129.51, 129.21, 128.54, 128.04, 127.47, 127.21, 124.59, 123.47, 123.07, 122.77, 121.91, 120.59, 120.08, 119.96, 110.49, 47.16, 27.16.

2-(9,9-Dimethyl-9H-indol-2-yl)-4-(4-(quinolin-8-yl)phenyl)quinazoline (Compound 5)

Benzylquinoline borate (3.000 g, 9.06 mmol), dichloroquinazoline (1.807 g, 9.08 mmol), and Pd(dppf)Cl ₂ (0.302 g, 0.41 mmol) were charged with a stir bar, A heating pack, a thermocouple, and a water condenser were placed in a 250 mL, three-neck round bottom flask with a nitrogen inlet. Rinse the flask with nitrogen, then add two that have been sprayed with nitrogen for 5 minutes. Alkane (120 mL). Ethanol (12 mL) and 40 wt% potassium phosphate tribasic (12 mL) in water were added. The reaction mixture was heated to 40 °C over 30 minutes at which time the first coupling was done by HPLC. Dimethyl decyl natto borate (2.901 g, 9.06 mmol) was added and the reaction was heated to 80 °C for 15 h. The reaction was allowed to cool to room temperature. The mixture was partitioned between methylene chloride (200 mL) and water (100 mL). The layers were separated and the aqueous layer was extracted with methylene chloride (100 mL). The combined organic layers were dried over magnesium sulfate, filtered, and concentrated by rotary evaporation to afford a dark brown solid. The solid was milled with ethyl acetate (75 mL) to remove a large amount of color. The material was dissolved in methylene chloride and concentrated on diatomaceous earth. This material was purified by normal phase flash chromatography (tetrahydrofuran/methylene chloride) to afford a white solid. The solid was triturated with ethyl acetate (75 mL) and dried in a vacuum oven (60 <0>C, 15h) to afford a final compound (3.30 g, 6.28 mmol, 69%) according to HPLC.

¹ H NMR (400 MHz, CDCl ₃ ) δ 9.03 (dd, J = 4.1, 1.8 Hz, 1H), 8.83 - 8.75 (m, 2H), 8.33 (d dd, J = 8.4, 0.8 Hz, 1H), 8.26 ( Dd, J = 8.3, 1.8 Hz, 1H), 8.22-8.17 (m, 1H), 8.11 - 8.04 (m, 2H), 8.01 - 7.94 (m, 2H), 7.94 - 7.83 (m, 4H), 7.83 7.78 (m, 1H), 7.67 (dd, J = 8.0,7.2Hz, 1H), 7.57 (ddd, J = 8.2,6.9,1.2Hz, 1H), 7.52-7.44 (m, 2H), 7.40-7.31 ( m, 2H), 1.62 (s, 6H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 168.13, 160.61, 154.69, 153.94, 152.17, 150.43, 146.03, 141.58, 141.37, 140.18, 138.88, 137.50, 136.72, 136.41, 133.44, 130.84, 130.56, 130.00, 129.13, 128.86, 128.17, 128.05, 127.65, 127.32, 127.01, 126.75, 126.40, 122.94, 122.69, 121.71, 121.20, 120.50, 120.01, 47.10, 27.24.

4-(9,9-Dimethyl-9H-indol-2-yl)-2-(4-(quinolin-8-yl)phenyl)quinazoline (Compound 6)

Benzquinoline borate (1.280 g, 3.86 mmol), mercaptoquinazoline (1.350 g, 3.78 mmol), and Pd(dppf)Cl ₂ (0.080 g, 0.11 mmol) were charged with a stir bar A heating pack, a thermocouple, and a water condenser with a nitrogen inlet of 250 mL, a three-necked round bottom flask. Rinse the flask with nitrogen, and add two that have been sprayed with nitrogen for 5 minutes. Alkane (60 mL). Ethanol (6 mL) and 40 wt% potassium phosphate tribasic (6 mL) in water were added. The reaction was heated to 80 ° C and stirred for 2 h. The reaction was allowed to cool to room temperature and partitioned between methylene chloride (100 mL) and water (25 mL). The layers were separated and the aqueous layer was extracted with methylene chloride (50 mL). The combined organic layers were dried over magnesium sulfate, filtered, and concentrated by rotary evaporation. The material was co-evaporated from ethyl acetate (50 mL) to afford a dark solid. The material was dissolved in methylene chloride, EtOAc (EtOAc) elute 2.13 mmol, 56%).

¹ H NMR (400 MHz, chloroform - d ) δ 8.99 (dd, J = 4.2, 1.8 Hz, 1H), 8.87 (d, J = 8.4 Hz, 2H), 8.21. (ddd, J = 9.8, 8.4, 1.6 Hz, 3H), 8.01 (dd, J = 1.4, 0.8 Hz, 1H), 7.98-7.87 (m, 5H), 7.86-7.80 (m, 3H), 7.64 (dd, J = 8.1, 7.2 Hz, 1H), 7.57 (ddd, J = 8.3, 6.9, 1.2 Hz, 1H), 7.53-7.47 (m, 1H), 7.47-7.36 (m, 3H), 1.61 (s, 6H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 168.44, 160.26, 154.30, 153.87, 152.25, 150.31, 146.14, 141.82, 140.63, 138.50, 137.22, 136.64, 136.23, 133.35, 130.87, 130.31, 129.60, 129.32, 128.79, 128.38, 127.96, 127.76, 127.18, 127.11, 126.82, 126.30, 124.76, 122.77, 121.85, 121.06, 120.57, 119.97, 47.17, 27.19.

Other inventive compounds can be formed using one or more of the reactions discussed above. Typically, the 2,4-dichloroquinazoline is first substituted at position 4 with a nucleophilic displacement or coupling reaction. The resulting substituted 2-chloroquinazoline is converted to the final product by Suzuki coupling with a suitable boric acid or other suitable coupling chemistry.

Modeling of the compounds of the invention and comparative compounds

In contrast to the comparative compounds, the compounds of the invention exhibit a preferred combination of suitable LUMO energy (-1.8 to -2.05 eV) and low recombination energy (λ ^- ) value (<0.30). Moreover, the compounds of the invention have a preferred molecular weight range of from 480 to 600 grams per mole which aids in the ability to purify such compounds by sublimation. The compounds of the invention also have high Tg (glass transition temperature) values which indicate good thermal stability.

OLED component manufacturing and testing

All organic materials are purified by sublimation before deposition. The OLED is fabricated on an ITO (indium tin oxide) coated glass substrate, the glass substrate is used as an anode, and the aluminum cathode is placed on top. All of the organic layers were thermally deposited by chemical vapor deposition using a base pressure of less than 10-7 Torr in a vacuum chamber. The deposition rate of the organic layer is maintained at 0.1 to 0.05 nm/second. The aluminum cathode system was deposited at 0.5 nm/sec. The effective area of the OLED element is "3 mm x 3 mm" as defined by the shadow mask for cathode deposition. The glass substrate (20 mm x 20 mm) was obtained from Samsung Corning and the ITO layer was 1500 angstroms thick.

A five-layer film is formed with the following configuration: ITO/hole injection material (HIL): 600Å/hole transport material (HTL): 200Å/doped 2% fluorescent green dopant fluorescent green body: 200Å/ Electron transport material (ETL: Liq) with lithium quinolate: 300 Å / electron injecting material (EIL): 10 Å / aluminum. The compounds used in each layer are listed in Table 3.

Each cell containing HIL, HTL, EML body, EML dopant, ETL, or EIL is placed inside the vacuum chamber until it reaches 10 ^-6 Torr. In order to evaporate various materials, a controlled current is applied to the chamber containing the material to raise the temperature of the chamber. Appropriate temperature is applied to maintain the evaporation rate of the material in the evaporation process constant.

In the case of the HIL layer, N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4- Diamine (N1-(naphthalen-2-yl)-N4, N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine) is constant at 1 angstrom The rate of /sec evaporates until the layer thickness reaches 600 angstroms. At the same time, N ⁴ , N ^{4 '} - bis(naphthalen-1-yl)- N ⁴ , N ^{4 '} -diphenyl-[1,1'-biphenyl]-4,4'-diamine (NPB) layer It was evaporated at a constant rate of 1 angstrom/second until the thickness reached 200 angstroms. In the aspect of the EML layer, 9,10-di(naphthalen-2-yl)anthracene (ADN, main body) and 9,10-di(naphthalen-2-yl)-N2, N2, N6, N6-tetraphenylphosphonium- The 2,6-diamine (dopant) was co-evaporated until the thickness reached 350 angstroms. The deposition rate of the host material was 0.98 Å/sec, and the deposition rate of the dopant material was 0.02 Å/sec, obtaining a 2% doped host material. In the case of the ETL layer, Compound 1 or Compound 2 is co-evaporated with lithium quinolate (Liq) in individual components until the thickness reaches 300 angstroms. The evaporation rate of Compound 1 or 2 of the present invention was 0.5 Å/sec each, and the evaporation rate of Liq was 0.5 Å/sec. Alq3 was used as a reference material for comparison with compounds 1 and 2. Alq3 was evaporated at a rate of 1 angstrom/second alone until the thickness reached 300 angstroms. Finally, a "20 angstrom" thin EIL (electron injection layer; here Liq) evaporates at a rate of 0.2 angstroms per second.

The current-voltage-luminance (J-V-L) characterization of the OLED elements was performed using a source measurement unit (KEITHLY 238) and a luminance meter (MINOLTA CS-100A). The EL spectrum of the OLED element was collected using a CCD spectrometer that had been calibrated.

result

Compounds 1 and 2 were each tested in a fluorescent green OLED. The results are shown in Table 4 below. The present invention comprises a film comprising an ETL (electron transport layer) film layer of Compound 1 or Compound 2, which exhibits a lower "turn on voltage" and a higher luminous efficiency than the reference film.

Claims (15)

A composition comprising at least one compound selected from the group consisting of (A, B, C, and D): A) Wherein R1 is selected from the group consisting of: i) a (C6-C40) aryl group with or without a substituent, or ii) a (C3-C40) heteroaryl group with or without a substituent; wherein R2 is selected from the group consisting of : i) a (C6-C40) aryl group with or without a substituent, or ii) a (C3-C40)heteroaryl group with or without a substituent, and wherein R3 is selected from the group consisting of: i) hydrogen or hydrazine , ii) (C1-C20)alkyl, iii) (C6-C40) aryl with or without a substituent, or iv) (C3-C40)heteroaryl with or without a substituent, and Formula 1 thereof Including at least three CN double bonds; and one or more of the hydrogens may be optionally substituted by deuterium; B) Wherein R1' is selected from the group consisting of: i) a (C6-C40) aryl group with or without a substituent, or ii) a (C3-C40) heteroaryl group with or without a substituent; wherein R2' is selected from In the following: i) hydrogen or hydrazine, ii) (C1-C20) alkyl, i) (C6-C40) aryl with or without a substituent, or iv) with or without a substituent (C3-C40) a heteroaryl group; wherein R3' and R4' are independently selected from the group consisting of: i) hydrogen or hydrazine, ii) (C1-C20) alkyl group, iii) (C6-C40) aryl with or without a substituent Or iv) a (C3-C40)heteroaryl group with or without a substituent; wherein R5' is selected from the group consisting of: i) hydrogen or hydrazine, ii) (C1-C20) alkyl, iii) with or Unsubstituted (C6-C40) aryl, or iv) (C3-C40)heteroaryl with or without a substituent, wherein L comprises (C6-C30)arylene or (C3-C30) a heteroaryl group; and wherein if R1' comprises biphenyl, it does not comprise a carbazole; and wherein one or more hydrogens are optionally substituted by deuterium; Wherein R1" is selected from the group consisting of: i) a (C6-C40) aryl group with or without a substituent, or ii) a (C3-C40) heteroaryl group with or without a substituent; wherein R2" is selected from In the following: i) hydrogen or hydrazine, ii) (C1-C20) alkyl, iii) (C6-C40) aryl with or without a substituent, or iv) with or without a substituent (C3-C40) a heteroaryl group; wherein R3" and R4" are independently selected from the group consisting of: i) hydrogen or hydrazine, ii) (C1-C20) alkyl group, iii) (C6-C30) aryl with or without a substituent Or iv) a (C3-C30)heteroaryl group with or without a substituent; wherein R5" is selected from the group consisting of: i) hydrogen or hydrazine, ii) (C1-C20) alkyl, iii) with or An unsubstituted (C6-C40) aryl group, or iv) a (C3-C40)heteroaryl group with or without a substituent; and wherein if R1" comprises biphenyl, it does not comprise a carbazole; Or a plurality of hydrogens may be optionally substituted by deuterium; and D) a combination thereof. The composition of claim 1, wherein the at least one compound is selected from the group consisting of Formula 1. The composition of claim 2, wherein R1 is selected from the group consisting of: The composition of claim 2 or claim 3, wherein R2 is selected from the following: The composition of any one of claims 2 to 4, wherein R1 comprises greater than or equal to 9 carbon atoms. The composition of any one of claims 2 to 5, wherein R2 comprises greater than or equal to 9 carbon atoms. The composition of claim 1, wherein the at least one compound is selected from the group consisting of Formula 2. The composition of claim 7, wherein R1' is selected from the group consisting of: The composition of claim 7 or claim 8, wherein L is selected from the group consisting of phenyl or naphthalene. The composition of any one of claims 7 to 9, wherein R1' comprises greater than or equal to 9 carbon atoms. The composition of any one of claims 7 to 10, wherein R2' and R5' are each hydrogen, and R3' and R4' are each a methyl group. The composition of claim 1, wherein the at least one compound is selected from the group consisting of Formula 3. The composition of claim 12, wherein R1" is selected from the group consisting of: The composition of claim 1, wherein the at least one compound is selected from the group consisting of the following compounds: An electronic component comprising at least one component formed by the composition of any one of claims 1 to 14.