TWI605055B - Phenoxaphosphine compounds - Google Patents

Description

Phenylphosphine compound

The invention relates to a kind of brown Phosphine compound.

Background of the invention

An organic light emitting element (OLED) is a display device using a film stack containing an organic aromatic compound as an electroluminescent layer. Such compounds are generally classified into electroluminescent materials and charge transport materials. Several properties required for this electroluminescent and charge transporting compound include high fluorescence quantum yield in solid state, high electron and hole mobility, chemical stability during vapor deposition in vacuum, and formation of a stable film. ability.

Common problems with OLEDs include rapid aging/short life, undesirably high operating voltages or insufficient efficiency. New materials for electron transport layers (ETL) and hole transport layers (HTL) for organic light-emitting diodes (OLEDs) have been found to improve component performance and life cycle goals. In the case of HTL layers, the state of the art technology uses a triarylamine base material that meets many of today's fluorescent and phosphorescent OLED designs. In the design of phosphorescent OLEDs, there are still problems of component efficiency, life cycle and brightness for the mass production of blue phosphorescent OLEDs. Therefore, there is a need for a hole transport layer that has an improved property relative to the current technology. Furthermore, the charge will be compared There is a need for a hole transport material that is fast to the emissive layer and that can have long lasting and high efficiency components. These needs and others have been met by the following inventions.

Summary of invention

The present invention provides a composition comprising at least one compound selected from the group consisting of: A) Wherein, for Formula A, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently a hydrocarbon or a substituted hydrocarbon; and 2 or more thereof are selected from R2, R3 The R groups of R4, R5, R6, R7, R8, R9 and R10 may form one or more ring structures selectively; B) Wherein, for Formula B, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently a hydrocarbon or a substituted hydrocarbon; and 2 or more thereof are selected from R1, R2 The R groups of R3, R4, R5, R6, R7, R8 and R9 may optionally form one or more ring structures; or C) combinations thereof.

Detailed description

Central morphine A new molecular group dominated by phosphine cores. This molecule can be adjusted by: 1) adjusting at the center of the phosphorus or along the brown An organic group at the position of the phosphine core; and 2) an oxidation state of the phosphorus center. The computational model of these derivatives suggests that the charge transport layer containing these compounds possesses a higher triplet state while maintaining the desired HOMO and LUMO energy levels. Furthermore, the arylamine substitution at the positions of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ leaves the HOMO orbital of the benzene ring traversing these substituents undetermined. Domainization. As a result, the excitons formed in the OLED element should be well confined to the emissive layer, and allow for improved component brightness, life cycle, and efficiency.

As discussed above, the present invention provides a composition comprising at least one compound selected from the group consisting of: A) Wherein, for Formula A, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently a hydrocarbon (including H) or a substituted hydrocarbon; and 2 or more thereof are selected from The R groups of R2, R3, R4, R5, R6, R7, R8 and R9 may form one or more ring structures selectively; B) Wherein, for Formula B, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently a hydrocarbon (including H) or a substituted hydrocarbon; and 2 or more thereof are selected from The R groups of R1, R2, R3, R4, R5, R6, R7, R8 and R9 may optionally form one or more ring structures; or C) combinations thereof.

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

As used ^{herein, R1 = R 1, R2 =} R 2, R3 = R 3 and the like.

In one embodiment, for Formula A, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are each independently a hydrocarbon or a substituted hydrocarbon; and for Formula B, R1 And R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each independently a hydrocarbon or a substituted hydrocarbon.

In one embodiment, for Formula A, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are each independently hydrogen, alkyl, substituted alkyl, aryl, a substituted aryl, heteroaryl or substituted heteroaryl; For formula B, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, hetero Aryl or substituted heteroaryl.

In one embodiment, for Formula A, R2, R4, R5, R6, R7, and R9 are each hydrogen; and for Formula B, R2, R4, R5, R6, R7, and R9 are each hydrogen. .

In one embodiment, for Formula A, R3 and R8 are each independently alkyl, and further C1-C8 alkyl, and further C1-C4 alkyl, and further ethyl or methyl. And for the formula B, R3 and R8 are each independently an alkyl group, and further a C1-C8 alkyl group, and further a C1-C4 alkyl group, and further an ethyl group or a methyl group.

In one embodiment, for Formula A, at least one of R2, R3, R4, R5, R6, R7, R8, and R9 is an arylamine; and for Formula B, R2, R3, R4, R5, At least one of R6, R7, R8 and R9 is an arylamine.

In one embodiment, for Formula A, R1 comprises at least six carbon atoms; and for Formula B, R1 comprises at least six carbon atoms.

In one embodiment, the composition comprises a compound of formula A and a compound of formula B.

In one embodiment, the at least one compound is selected from the group consisting of: , Or a combination thereof.

In one embodiment, the at least one compound is selected from Formula A.

In one embodiment, for Formula A, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are each independently a hydrocarbon or a substituted hydrocarbon.

In one embodiment, for Formula A, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are each independently hydrogen, alkyl, substituted alkyl, aryl, Substituted aryl, heteroaryl or substituted heteroaryl.

In one embodiment, for Formula A, R2, R4, R5, R6, R7, and R9 are each hydrogen.

In one embodiment, for Formula A, R3 and R8 are each independently alkyl, and further C1-C8 alkyl, and further C1-C4 alkyl, and further ethyl or methyl. .

In one embodiment, for Formula A, at least one of R2, R3, R4, R5, R6, R7, R8, and R9 is an arylamine.

In one embodiment, for Formula A, R1 comprises at least six carbon atoms.

In one embodiment, for Formula A, each R1 further comprises at least one oxygen atom or at least one nitrogen atom.

In one embodiment, for Formula A, R1 further comprises at least 12 carbon atoms.

In one embodiment, the at least one compound is selected from the group consisting of: Or a combination thereof.

The compound of formula A may comprise two or more combinations as specific examples described herein.

In one embodiment, the at least one compound is selected from Formula B.

In one embodiment, for Formula B, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are each independently a hydrocarbon or a substituted hydrocarbon.

In one embodiment, for Formula B, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are each independently hydrogen, alkyl, substituted alkyl, aryl, Substituted aryl, heteroaryl or substituted heteroaryl.

In one embodiment, for Formula B, R2, R4, R5, R6, R7, and R9 are each hydrogen.

In one embodiment, for Formula B, R3 and R8 are each independently alkyl, and further C1-C8 alkyl, and further C1-C4 alkyl, and further ethyl or methyl.

In one embodiment, for Formula B, at least one of R2, R3, R4, R5, R6, R7, R8, and R9 is an arylamine.

In one embodiment, for Formula B, R1 comprises at least six carbon atoms.

In one embodiment, for Formula B, each R1 further comprises at least one oxygen atom or at least one nitrogen atom.

In one embodiment, for Formula B, R1 further comprises at least 12 carbon atoms.

In one embodiment, the at least one compound is selected from the group consisting of: , Or a combination thereof.

The compound of formula B may comprise two or more combinations as specific examples described herein.

In one embodiment, the at least one compound has a molecular weight greater than or equal to 400 grams per mole, and further greater than or equal to 500 grams per mole.

In one embodiment, the at least one compound has a molecular weight greater than or equal to 600 grams per mole, and further greater than or equal to 700 grams per mole.

In one embodiment, the at least one compound has a HOMO energy system of from -4.7 electron volts to -5.6 electron volts.

In one embodiment, the at least one compound has The LUMO energy system is -1.0 eV to -3.0 eV.

In a specific embodiment, the composition of any of the preceding claims, wherein the at least one compound has a triplet energy system of 2.00 eV to 4.00 eV.

In one embodiment, the at least one compound has a sublimation temperature greater than or equal to 200 °C.

In one embodiment, the at least one compound comprises one or more deuterium atoms.

The compounds of the invention may comprise two or more combinations as specific examples described herein.

In one embodiment, the composition further comprises a metal quinolate. In a further embodiment, the metal is faster than lithium.

In one embodiment, the composition comprises from 10 to 90 weight percent, further from 10 to 70 weight percent of the metal, based on the weight of the composition. In a further embodiment, the composition comprises from 10 to 50 weight percent of the metal, based on the weight of the composition. In a further embodiment, the composition comprises from 20 to 50 weight percent of the metal, based on the weight of the composition.

In one embodiment, the composition comprises from 10 to 90 weight percent, further from 10 to 70 weight percent of lithium, based on the weight of the composition. In a further embodiment, the composition comprises from 10 to 50 weight percent lithium fasting based on the weight of the composition. In a further embodiment, the composition comprises from 20 to 50 weight percent lithium Faster, based on the weight of the composition.

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

The invention also provides a film comprising at least one layer formed from one or more of the compositions of the invention described in the specific examples herein.

The invention also provides an electronic device comprising at least one film layer formed from one or more of the compositions of the invention described in the specific examples herein.

The invention also provides an electronic device comprising at least one member formed from one or more of the compositions of the invention described in the specific examples herein.

The compositions of the present invention are useful in applications in organic light emitting diodes (OLEDs) or related organic electronic devices, including organic solar cells. More particularly, the compositions of the present invention find applications in various layers of OLEDs, including HIL (hole injection layer), HTL (hole transport layer), EML (emitter layer, including host and dopant), ETL (Electronic Transport Layer).

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

Elements of the invention may comprise two or more combinations as specific examples described herein.

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

The at least one compound may comprise two or more combinations as specific examples described herein.

A compound of formula A may comprise two or more combinations as specific examples described herein.

A compound of formula B may comprise two or more combinations as specific examples described herein.

The synthesis of the population of hole transport materials of the present invention typically requires the preparation of appropriately substituted 10-chloromorphs. phosphine. These molecules react with appropriately substituted nucleophiles to produce the desired form Phosphine species. If necessary, H ₂ O _{2 can} oxidize the film Phosphine derivatives to produce substituted brownies Phosphine 10-oxide. Substituted 10-chloromorphine The synthesis of phosphines can be accomplished following existing techniques using commercially available diaryl ethers, AlCl3 and PCl3 (Vedejs, E.; Marth, CFJAm. Chem. Soc. 1988, 110, 3948-3958). In order to produce a derivative having a phosphorus-C (aryl) interaction, the 10-chloromorph The phosphine system is reacted with an aryl lithium reagent. In the case of a phosphorus-O linkage, the 10-chloromorph The phosphines are reacted with a substituted phenol in the presence of a base to produce the desired product. The corresponding brown The phosphine 10-oxide is synthesized by the reaction of these products with H ₂ O ₂ . Immune Depending on the R substitution of the phosphine 10-oxide, these molecules can be further derivatized to produce a hole transporting molecule. See, for example, the following reaction scheme.

As used herein, the term "hydrocarbon" means only carbon and hydrogen. A chemical group of an atom (H and C; H; or C). As used herein, the term "hydrocarbon" includes hydrogen.

As used herein, the term "substituted hydrocarbon" is intended to mean that one or more hydrogens are each independently substituted with another group comprising at least one hetero atom, and/or one or more carbons are independently Another hydrocarbon substituted with a group containing at least one hetero atom.

As used herein, the term "aryl" refers to an organic radical derived from an aromatic hydrocarbon. The aryl group may be a monocyclic and/or fused ring system, each ring suitably containing from 4 to 7, preferably 5 or 6 ring atoms. Also included is a structure in which two or more aryl groups are bonded via a single bond. Particular embodiments include phenyl, naphthyl, biphenyl, anthracenyl, fluorenyl, fluorenyl, phenanthryl, triphenylene, fluorenyl, fluorenyl, The group is a condensed tetraphenyl group, an allyl group, and the like, but is not limited thereto. The naphthyl group may be 1-naphthyl or 2-naphthyl; the fluorenyl group may be a 1-indenyl group, a 2-indenyl group or a 9-fluorenyl group; and the fluorenyl group may be a 1-indenyl group or a 2-indenyl group. Any of 3-mercapto, 4-indenyl and 9-fluorenyl.

As used herein, the term "heteroaryl" refers to a heteroatom comprising at least one selected from, for example, B, N, O, S, P(=O), Si, and P, for use in an aromatic cyclic backbone. An atom; and a carbon atom for the aryl group of the remaining aromatic cyclic skeleton atom. The heteroaryl group can be a 5 or 6 membered monocyclic heteroaryl or polycyclic heteroaryl group fused to one or more benzene rings and partially saturated. Also included are structures having one or more heteroaryl groups 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. Particular embodiments include, but are not limited to, monocyclic heteroaryls such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isomeric Azolyl, Azolyl, Diazolyl, three Base, four Base, triazolyl, tetrazolyl, furazolyl, pyridyl, pyridyl Base, pyrimidinyl, oxime Polycyclic heteroaryl such as benzofuranyl, benzothienyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benziso Azolyl, benzo Azolyl, isodecyl, fluorenyl, oxazolyl, benzothia-oxadiazolyl, quinolyl, isoquinolyl, Porphyrin, quinazolinyl, quinoxalinyl, oxazolyl, phenanthryl and benzodiazepine a mercapto group; and a corresponding N-oxide (eg, pyridyl N-oxide, quinolinyl N-oxide) and a quaternary salt thereof.

Examples of substituents include the following: hydrazine, halogen, (C1-C30)alkyl with or without a halogen substituent, (C6-C30) aryl, with or without (C6-C30) aryl substituent (C3-C30)heteroaryl, 5- to 7-membered heterocycloalkyl containing one or more heteroatoms selected from, for example, B, N, O, S, P(=O), Si, and P, and Or a plurality of aromatic ring fused 5 to 7 membered heterocycloalkyl groups, (C3-C30)cycloalkyl group, (C6-C30) cycloalkyl group fused to one or more aromatic rings, and tris(C1-C30) Alkylalkyl, di(C1-C30)alkyl(C6-C30)aryldecyl,tri(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 [where R ₂ i To R ₂₈ each independently represents (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl], (C6-C30)ar(C1-C30)alkyl, (C1- C30) alkyl (C6-C30) aryl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C6-C30) aryloxy, (C6-C30) arylthio, (C1 -C30) alkoxycarbonyl, (C1-C30)alkylcarbonyl, (C6-C30)arylcarbonyl, (C6-C30)aryloxycarbonyl, (C1-C30)-alkane Alkylcarbonyloxy, (C1-C30)alkylcarbonyloxy, (C6-C30)arylcarbonyloxy, (C6-C30)-aryloxycarbonyloxy, carboxy, nitro and hydroxy; or contiguous The substituents are joined together to form a ring.

experiment Reagents and test methods

All solvents and reagents are obtained in commercially available quality purum, puriss or analytical grade (p.a.). Dry solvents were obtained from an in-house purification/dispensing system (hexane, toluene, tetrahydrofuran and diethyl ether) or purchased from Sigma-Aldrich. All experiments involving water-sensitive compounds were carried out in oven-dried glassware under a large nitrogen atmosphere or in a nitrogen box. The reaction was monitored by pre-coated aluminum plates (VWR 60 F254) by analytical thin layer chromatography (TLC) and stained by UV light and/or potassium permanganate. Flash chromatography was performed on an ISCO COMBIFLASH system containing GRACERESOLV(R).

1H-NMR-spectroscopy (500 MHz or 400 MHz) was obtained on a Varian VNMR S-400 spectrometer at 30 ° C unless otherwise mentioned. The chemical shift is referred to one of the following: TMS in CHCl3 (δ = 0.00) in CDCl3. If necessary, peak assignment is performed with the help of COSY, HSQC or NOESY experiments.

The 13C spectrum (125 MHz or 100 MHz) was obtained on a VNRMS-400 spectrometer solvent or standard signal (0.0-TMS in CDCl3).

A routine LC/MS study was performed as follows. Five microliters of the sample was injected onto an Agilent 1200SL binary gradient liquid chromatograph, where the fraction was "3 mg/ml in THF", where the chromatograph was The Agilent 6520 QT's quadrupole time-of-flight MS system is coupled in PI mode via a dual-spray electrospray (ESI) interface. The following analytical conditions were used: column: 150 x 4.6 mm ID 3.5 micron Zorbax SB-C8; column temperature: 40 ° C; mobile phase: 75/25 A/B to 15/85 A/B at 40 minutes; solvent A =0.1v% formic acid in water; solvent B = THF; flow 1.0 ml / min; UV detection: 210 to 600 nm diode array (extraction wavelength 250,280 nm); ESI conditions: gas temperature 365 ° C ; gas flow - 8 ml / min; capillary - 3.5 kV; nebulizer - 40 psi; fragmentor - 145 volts.

Cyclic voltammetry measurements were performed using a WaveNano potentiostat (Pine Research Instrumentation). Silver/nitric acid silver (silver wire immersed in freshly prepared 5 mM silver nitrate solution in anhydrous acetonitrile containing 0.1 M TBAP as supporting electrolyte), platinum wire and platinum disk (1.6 mm diameter) were used as reference, counter and working electrodes. A total oxidation scan was measured on approximately 5 mM of the analyte solution in DCM (anhydrous), which contained 1 M TBAP as a supporting electrolyte; a 5 mM solution in THF (anhydrous, no inhibitor) was subjected to a total reduction scan, wherein the solution Contains 0.1M TBAP. Typically, 3 cycles (6 segments) are performed at a scan rate of 20 millivolts per second. The energy level is corrected by compensating for 4.7 volts to convert to a vacuum level.

The DSC was performed using a 2000 instrument at a scan rate of 10 ° C/min, and all cycles were in a large nitrogen atmosphere. The sample (about 7-10 mg) was scanned from room temperature to 300 ° C, cooled to -60 ° C, and reheated to 300 ° C. The glass transition temperature (T _g ) was measured during the second heating scan. Data analysis was performed using the TA Universal Analysis software. The T _g is calculated using the "recurved midpoint" method.

model

All calculations use the Gaussian 09 program ¹ . The calculations were performed using a hybrid density functional theory (DFT) method, B3LYP ² and 6-31G* (5d) basis setting ³ . The singlet state calculation uses a closed shell approximation, and the triplet calculation uses an open shell approximation. All values refer to electron volts (eV). The HOMO and LUMO values are measured from the orbital energy of the optimized geometry of the single ground state. The triplet state is measured as the difference between the optimized triplet state and the total energy of the optimized singlet state.

1. Gaussian 09, Revision A.02, Frisch, MJ; Trucks, GW; Schlegel, HB; Scuseria, GE; Robb, MA; Cheeseman, JR; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson , GA; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, HP; Izmaylov, AF; Bloino, J.; Zheng, G.; Sonnenberg, JL; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, N.; Vreven, T.; Montgomery, Jr., JA; Peralta, JE; Ogliaro, F.; Bearpark, M.; Heyd, JJ; Brothers, E.; Kudin, KN; Staroverov, VN; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.;Burant,JC;Iyengar,SS;Tomasi,J.;Cossi,M.;Rega,N.;Millam,JM;Klene,M.;Knox,JE;Cross,JB;Bakken,V.;Adamo, C.;Jaramillo,J.;Gomperts,R.;Stratmann,RE;Yazyev,O.;Austin,AJ;Cammi,R.;Pomelli,C.;Ochterski,JW;Martin, RL;Morokuma,K.;Zakrzewski , VG; Voth, GA; Salvador, P. Dannenberg, JJ; Dapprich, S;. Daniels, AD; Farkas, O;. Foresman, JB; Ortiz, JV; Cioslowski, J;. Fox, DJ, 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) Ditehfield, 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.

4-(2,8-dimethyl-10H-morphine Preparation of phosphino-10-yl)-N,N-diphenylaniline

In a solution of 4-bromotriphenylamine (5.00 g, 15.4 mmol) in diethyl ether (100 ml) cooled to 0 ° C, 1.6 M nBuLi (10.6) was added dropwise over a period of 15 minutes. ML, 17.0 millimoles). The cooled solution was stirred at this temperature for one hour and then cooled to -78 °C. At this temperature, 10-chloro-2,8-dimethyl-10H-morphine was added dropwise A solution of phosphine (4.45 g, 17.0 mmol) in tetrahydrofuran (20 mL), after which the suspension was allowed to gradually warm to room temperature. After stirring overnight, the suspension was filtered through a plug of plastic stopper and the solvent was removed to dryness. Toluene (100 mL) was added to the residue, and the suspension was stirred for 5 min. Again, the suspension was filtered through a plug of celite, and the volume of the solvent was reduced to 30 ml, then hexanes (30 ml) was added to precipitate a white solid, which was collected by filtration (yield = 6.50 g, 89.3%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 2.32 (s, 6H), 6.87 (d, J = 8 Hz, 2H), 6.99-7.08 (m, 8H), 7.11-7.17 (m, 4H), 7.19-7.24 (m, $H), 7.29 (d, J = 8 Hz).

¹³ C{ ¹ H} NMR (CDCl ₃ ) δ 20.6, 117.4, 117.7, 122.0 (d, J = 8 Hz), 128.4, 125.0, 129.2, 131.5, 132.7, 132.8, 133.1 (d, J = 25 Hz), 134.8 (d, J = 41 Hz), 147.1, 148.3, 153.2.

³¹ P{ ¹ H} NMR (CDCl ₃ ) δ -52.9.

T _g = 61.3 ° C. HOMO: measured value - 5.3 volts; LUMO: measured value - 2.1 volts.

10-(4-(diphenylamino)phenyl)-2,8-dimethyl-10H-morphine Preparation of phosphine 10-oxide

In 4-(2,8-dimethyl-10H-morphine Phosphino-10-yl) -N, N- diphenyl aniline (8.00 g, 17.0 mmol) in CH ₂ Cl ₂ (50 ml) was added 30% aqueous H ₂ O ₂ (6 mL). The biphasic mixture was stirred at room temperature overnight, followed by the addition of 5 ml of water. The organic fraction was separated, dried MgSO _4, and solvent was removed by rotary evaporation. The product was recrystallized from boiling MeOH (mass = 8.15 g, 98.5%). T _g = 89.5 ° C.

¹ H NMR (400 MHz, CDCl ₃ ) δ 2.34 (s, 6H), 6.96 (d, J = 4 Hz, 2H), 7.09-7.12 (m, 6H), 7.20 (dd, J = 4, 8 Hz, 2H ), 7.25-7.29 (m, 4H), 7.33 - 7.39 (m, 4H), 7.58 (d, J = 12 Hz, 2H).

¹³ C{ ¹ H} NMR (CDCl ₃ ) δ 20.6, 114.7, 115.7, 117.9 (d, J = 8 Hz), 119.8 (d, J = 16 Hz), 124.5, 125.9, 129.5, 130.7, 132.4 (d, J = 14 Hz), 133.4 (d, J = 12 Hz), 134.6, 146.5, 150.8, 153.7.

³¹ P{ ¹ H} NMR (CDCl ₃ ) δ 1.1.

T _g = 89.5 ° C. HOMO: measured value - 5.5 volts; LUMO: measured value - 2.1 volts. Purity after sublimation (LC-MS): 99.6%

4-((2,8-dimethyl-10H-morphine) Preparation of phosphino-10-yl)oxy)-N,N-diphenyl-aniline

In 10-chloro-2,8-dimethyl-10H-morphine Phosphine (1.85 g, 7.05 mmol) in toluene (50 mL) was added an excess of NEt ₃ (10 mL) followed by 4- (diphenyl amino) phenol (1.84 g, 7.05 mmol) in toluene (20 ml) solution. During the addition, a large amount of colorless precipitate was formed which was stirred at room temperature overnight. Have suspension was filtered through Celite, and the solvent removed in vacuo to provide an off-white residue from Et ₂ O / hexanes recrystallization, to provide a colorless solid (3.32 g, 96.6%).

^{_{1 H NMR (400MHz, CDCl 3}} ) δ 2.48 (s, 6H), 6.33 (d, J = 4 Hz, 2H), 6.83 (d, J = 4 Hz, 2H), 7.00-7.06 (m, 6H), 7.17 (d, J = 8 Hz, 2H), 7.24 - 7.37 (m, 4H), 7.30 (dd, J = 4, 8 Hz, 2H), 7.73 (d, J = 12 Hz, 2H).

¹³ C{ ¹ H} NMR (CDCl ₃ ) δ 20.6, 117.6, 118.2 (d, J = 20 Hz), 121.8 (d, J = 8 Hz), 122.0, 123.1, 126.1, 129.0, 132.5 (d, J = 20 Hz), 134.0, 135.5 (d, J = 40 Hz), 142.8, 147.6, 151.0 (d, J = 8 Hz), 152.2.

³¹ P{ ¹ H} NMR (CDCl ₃ ) δ 64.0. T _g = not observed.

10-(4-(diphenylamino)phenoxy)-2,8-dimethyl-10H-morphine Preparation of phosphine 10-oxide

In 4-((2,8-dimethyl-10H-morphine) Phosphino-10-yl) oxy) -N, N- diphenyl aniline (3.50 g, 7.18 mmol) in CH ₂ Cl ₂ (50 ml) was added 30% H ₂ O ₂ aqueous solution (3 ml ). The biphasic mixture was stirred overnight at room temperature, followed by the addition of 5 ml of water. The organic fraction was separated, dried MgSO _4, and solvent was removed by rotary evaporation. The product was recrystallized from boiling MeOH (yield = 3.52 g, 97.4%). T _g = 55.6 ° C.

^{_{1 H NMR (400MHz, CDCl 3}} ) δ 2.43 (s, 6H), 6.80 (d, J = 4 Hz, 2H), 6.94 (d, J = 4 Hz, 2H), 7.00-7.05 (m, 6H), 7.21-7.28 (m, 4H), 7.30 (d, J = 8 Hz, 2H), 7.45 (dd, J = 4, 8 Hz, 2H), 7.75 (d, J = 12 Hz, 2H).

¹³ C{ ¹ H} NMR (CDCl ₃ ) δ 20.6, 112.4, 113.7, 118.2 (d, J = 12 Hz), 122.3 (d, J = 8 Hz), 112.6, 123.9, 125.4, 129.2, 133.2 (d, J = 12 Hz), 135.3, 144.8, 145.8 (d, J = 12 Hz), 147.7, 155.2.

³¹ P{ ¹ H} NMR (CDCl ₃ ) δ 0.5.

T _g = 55.6 ° C. HOMO: measured value - 5.5 volts; LUMO: measured value - 2.1 volts. Purity after sublimation (LC-MS): 99.8%.

N ² , N ² , N ⁸ , N ⁸ , 10-pentaphenyl-10H-morphine Preparation of phosphine-2,8-diamine

In a 250 ml round bottom flask, diphenylamine (5.26 g, 31.1 mmol), 2,8-dibromo-10-phenyl 10H-morphine were added under N ₂ Phosphine 10-oxide (3.50 g, 7.77 mmol), tertiary sodium butoxide (1.79 g, 18.7 mmol) and 100 mL toluene. Was added dropwise Pd (OAc) ₂ (70 mg, 0.31 mmol) and P ^t Bu ₃ (126 mg, 0.62 mmol) in toluene, and the mixture was heated to reflux overnight. After cooling to room temperature, the organic solvent was removed by rotary evaporation to give a dark residue. The residue was dissolved in 200 mL of CH ₂ Cl ₂ and 100 mL brine and organic fractions were collected. To 2x100 mL CH ₂ Cl ₂ washed with water, and the organic fractions were combined and dried MgSO _4. The suspension was filtered and the organic solvent was removed by rotary evaporation. This was recrystallized from MeOH to provide a dark residue as a white crystalline solid lines by flash column chromatography (EtOAc in: hexanes; 1: 1) to afford ^{N 2, N 2, N 8} , N 8, 10-pentaphenyl-10H-morphine Phosphine-2,8-diamine as white solid (3.65 g, & 5%).

^{_{1 H NMR (400MHz, CDCl 3}} ) δ 6.97-7.02 (m, 12H), 7.17-7.24 (m, 10H), 7.29-7.31 (dd, J = 4,8 Hz, 2H), 7.40 (m, 2H) , 7.45-7.51 (m, 5H).

¹³ C{ ¹ H} NMR (CDCl ₃ ) δ 114.9, 115.7, 116.8, 118.6 (d, J = 14 Hz), 124.2, 125.0, 129.1, 129.6, 132.5 (d, J = 12 Hz), 132.7 (d, J = 14 Hz), 134.1, 146.0, 152.3 (d, J = 121 Hz), 154.9.

³¹ P{ ¹ H} NMR (CDCl ₃ ) δ 1.2.

T _g = 104 ° C. HOMO: measured value - 5.3 volts; LUMO: measured value - 2.1 volts. Purity after sublimation (LC-MS): 99.7%.

These compounds can be used in the film layer for OLED elements.

Claims (12)

A composition comprising at least one compound selected from the group consisting of: A) Wherein, for Formula A, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, a heteroaryl or substituted heteroaryl group, and at least one of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is an arylamine; and, optionally, 2 or more selected from The R groups of R2, R3, R4, R5, R6, R7, R8 and R9 may form one or more ring structures; Wherein, for Formula B, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, a heteroaryl or substituted heteroaryl group, and at least one of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is an arylamine; and, optionally, 2 or more selected from R groups of R1, R2, R3, R4, R5, R6, R7, R8 and R9 may form one or more ring structures; or C) ; or D) ; or E) ; or F) ; or G) a combination of these. The composition of claim 1, wherein, for the formula A, R2, R4, R5, R6, R7 and R9 are each hydrogen; and for the formula B, R2, R4, R5, R6, R7 and R9 are each One is hydrogen. The composition of claim 1, wherein, for the formula A, R3 and R8 are each independently an alkyl group; and for the formula B, each of R3 and R8 is an alkyl group. The composition of claim 1, wherein for formula A, R1 comprises at least six carbon atoms; and wherein for formula B, R1 comprises at least six carbon atoms. The composition of claim 1, wherein the composition comprises a compound of formula A and a compound of formula B. The composition of claim 1, wherein the at least one compound is selected from the group consisting of: Or a combination thereof. The composition of claim 1, wherein the at least one compound is selected from the group consisting of Formula A. The composition of claim 1, wherein the at least one compound is selected from the group consisting of: Or a combination thereof. The composition of claim 1, wherein the at least one compound is selected from the formula B. The composition of claim 1, wherein the at least one compound is selected from the group consisting of: Or a combination thereof. A film comprising at least one layer formed from the composition of any one of claims 1 to 10. An electronic device comprising at least one member formed from the composition of any one of claims 1 to 10.