Charge transporting semi-conducting material and electronic device comprising it

Abstract

The present invention relates to a charge transporting semi-conducting material comprising: a) at least one electrical dopant, and b) a branched or cross-linked charge-transporting polymer comprising cyclobutenone cross-linking units of at least one of the general formulae la and/or lb, wherein aa) Pol.sup.1, Pol.sup.2, Pol.sup.3 and Pol.sup.4 are independently selected chains of the charge-transporting polymer, bb) X.sup.1, X.sup.2, X.sup.3, and X.sup.4 are independently selected optional spacer units or, independently, represent direct bonding of Pol.sup.1, Pol.sup.2, Pol.sup.3 and Pol.sup.4 chains to the cyclobutenone ring, cc) Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 are independently selected from H, halogen or a carbon-containing group; the charge transporting semi-conducting material being obtainable by a process comprising: i) providing a solution containing aaa) at least one precursor charge transporting compound comprising at least one covalently attacked alkenyloxy group having generic formula II wherein X is an optional spacer which is further linked to a charge transporting structural moiety of the precursor charge transporting compound, the dashed line represents the bonding to a charge transporting structural moiety of the precursor charge transporting compound and Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 are independently selected from H, halogen or the carbon-containing group, bbb) at least one electrical dopant, ccc) at least one solvent, ii) depositing the solution on a substrate, iii) removing the solvent, and iv) reacting the alkinyloxy groups to effect crosslinking, preferably by heating, wherein the average number of the alkinyloxy groups per one molecule of the precursor charge transporting compound provided in the step i) is equal to or greater than 2, preferably greater than 2.05, and a process for preparing the same.

Claims

1. Charge transporting semi-conducting material comprising: a) at least one electrical dopant, and b) a branched or cross-linked charge-transporting polymer comprising cyclobutenone cross-linking units of at least one of the general formulae Ia and/or Ib, ##STR00042## wherein aa) Pol.sup.1, Pol.sup.2, Pol.sup.3 and Pol.sup.4 are independently selected chains of the charge-transporting polymer, bb) X.sup.1, X.sup.2, X.sup.3, and X.sup.4 are independently selected optional spacer units or, independently, represent direct bonding of Pol.sup.1, Pol.sup.2, Pol.sup.3 and Pol.sup.4 chains to the cyclobutenone ring, and cc) Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 are independently selected from H, halogen or a carbon-containing group.

2. Charge transporting semi-conducting material according to claim 1, wherein the electrical dopant is a p-dopant or an n-dopant.

3. Charge transporting semi-conducting material according to claim 1, wherein the electrical dopant is selected from (i) [3]-radialene compounds, wherein each bridgehead carbon atom is substituted by a nitrile group, C.sub.6-C.sub.14 perfluorinated aryl or C.sub.2-C.sub.14 perfluorinated heteroaryl, wherein up to three fluorine atoms in the perfluorinated substituents may optionally be replaced by groups independently selected from nitrile or trifluoromethyl, and/or (ii) unsubstituted or substituted oxazolyl, diazolyl and/or thiazolyl radicals.

4. Electronic device comprising a semi-conducting layer comprising the charge transporting semi-conducting material according to claim 1.

5. A charge transporting semi-conducting material obtained by a process comprising: i) providing a solution containing aaa) at least one precursor charge transporting compound comprising at least one covalently attached alkinyloxy group having generic formula II ##STR00043## wherein X is an optional spacer which is further linked to a charge transporting structural moiety of the precursor charge transporting compound, the dashed line represents the bonding to a charge transporting structural moiety of the precursor charge transporting compound, and Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 are independently selected from H, halogen or the carbon-containing group, bbb) at least one electrical dopant, ccc) at least one solvent, ii) depositing the solution on a substrate, iii) removing the solvent, and v) reacting the alkinyloxy groups to effect crosslinking, wherein the average number of the alkinyloxy groups per one molecule of the precursor charge transporting compound provided in the step i) is equal to or greater than 2.

6. Charge transporting semi-conducting material according to claim 5, wherein the precursor charge transporting compound is a precursor charge transporting oligomer or a precursor charge transporting small molecule.

7. Charge transporting semi-conducting material according to claim 5, wherein the precursor charge transporting compound is a charge transporting polymer which comprises ethylene building units substituted with at least one pending side group comprising at least one charge transporting structural moiety which comprises a conjugated system of at least 4 delocalized electrons.

8. Charge transporting semi-conducting material according to claim 5, wherein the charge transporting structural moiety is comprised in a carbocyclic or heterocyclic structural moiety.

9. Charge transporting semi-conducting material according to claim 8, wherein the charge transporting structural moiety comprises an aromatic system of delocalized electrons.

10. Charge transporting semi-conducting material according to claim 9, wherein the charge transporting structural moiety comprises at least two rings which are independently selected from aromatic and heteroaromatic rings.

11. Charge transporting semi-conducting material according to claim 5, wherein the charge transporting structural moiety comprises at least one trivalent nitrogen atom.

12. Charge transporting semi-conducting material according to claim 11, wherein the trivalent nitrogen atom is substituted with three carbocyclic or heterocyclic rings which are independently selected from aromatic and heteroaromatic rings.

13. Charge transporting semi-conducting material according to claim 5, wherein the charge transporting structural moiety is selected from the group consisting of ##STR00044## ##STR00045## wherein the dashed line represents the covalent bond to the rest of the charge transporting polymer.

14. Crosslinked charge transporting polymer which is formed from the precursor charge transporting oligomer and/or from the precursor charge transporting small molecule as defined in claim 6.

15. Charge transporting semi-conducting material according to claim 5, wherein the average number of the alkinyloxy groups per one molecule of the precursor charge transporting compound provided in the step i) is equal to or greater than 2.05.

16. Charge transporting semi-conducting material according to claim 5, wherein the reacting of the alkinyloxy groups to effect crosslinking comprises heating.

17. Process for preparing a charge transporting semi-conducting material, the process comprising: i) providing a solution containing a) a precursor charge-transporting compound comprising at least one covalently attached alkinyloxy group having formula II ##STR00046## wherein X is the optional spacer which is further linked to a charge transporting structural moiety of the precursor charge transporting compound, the dashed line represents the bonding to the charge transporting structural moiety of the precursor charge transporting compound and Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 are independently hydrogen, halogen or a carbon-containing group, b) at least one electrical dopant, c) at least one solvent, ii) depositing the solution on a substrate, iii) removing the solvent, and iv) reacting the alkinyloxy groups to effect crosslinking, wherein the average number of the substituted alkinyloxy groups having formula II per molecule in the precursor charge transporting compound is equal to or greater than 2.

18. Process according to claim 17, wherein the average number of the alkinyloxy groups per one molecule of the precursor charge transporting compound provided in the step i) is equal to or greater than 2.05.

19. Process according to claim 17, wherein the reacting of the alkinyloxy groups to effect crosslinking comprises heating.

20. Solution comprising: a) a precursor charge-transporting compound comprising at least one covalently attached alkinyloxy group having formula II ##STR00047## wherein X is the optional spacer which is further linked to a charge transporting structural moiety of the precursor charge transporting compound, the dashed line represents the bonding to the charge transporting structural moiety of the precursor charge transporting compound and Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 are independently hydrogen, halogen or a carbon-containing group, b) at least one electrical dopant, and c) at least one solvent.

21. Solution according to claim 20, wherein the solvent comprises at least 1 wt % of a nitrile compound.

Description

(1) In the following, the invention will be described in further detail, by the way of examples.

(2) The figures show:

(3) FIG. 1: Graph of current density of the blue OLED in dependence on the voltage;

(4) FIG. 2: Graph of luminance of the blue OLED in dependence on time.

EXAMPLES

(5) Several precursor charge transporting polymers and precursor charge transporting small molecules, listed in Tab. 1, were prepared and used for preparing the inventive charge transporting semiconducting material.

(6) TABLE-US-00001 TABLE 1 FL241 FL253 FL262 0 FL272 FL293 FL298 LRT269

(7) General Methods.

(8) Gel permeation chromatography (GPC) measurements of polymer molecular weights were carried out on Agilent 1100 Series (Agilent, USA) normal-temperature size exclusion chromatograph, equipped with a refractive index detector and one column PL Gel MIXED-B (Polymer Laboratories, U.K.); the eluent was tetrahydrofuran (THF), and the flow rate was 1 mL/min. Number-average molecular weights (Mn) and polydispersity indexes (PDI) of the obtained polymers were determined based on calibration with polystyrene standards obtained from Polymer Standards Service (PSS, Germany).

(9) Starting Materials for Polymer Preparation

N.SUP.4.-phenyl-N.SUP.4.,N.SUP.4.-di-m-tolyl-N.SUP.4.-(4-vinylphenyl)-[1,1-biphenyl]-4,4-diamine (TPD-monomer), (A)

(10) ##STR00024##

(11) Prepared according to Thesen, M. W. et al. Hole-transporting host-polymer series consisting of triphenylamine basic structures for phosphorescent polymer light-emitting diodes. J. Polym. Sci. Part Polym. Chem. 48, 3417-3430 (2010). [1]

N.SUP.1.-phenyl-N.SUP.4.-(4-(phenyl(m-toly)amino)phenyl)-N.SUP.1.-(m-tolyl)-N.SUP.4.-(4-vinylphenyl)benzene-1,4-diamine (MTDATA-Monomer), (B)

(12) ##STR00025##

(13) Prepared according to [1].

N,N-bis(4-(9H-carbazole-9-yl)phenyl)-4-vinylaniline (C)

(14) ##STR00026##

(15) Prepared according to [1].

1-ethoxy-5-iodopent-1-yne (1)

(16) ##STR00027##

(17) This synthesis was performed according to a modified procedure published by Hanna, R. & Daoust, B.: Intramolecular regioselective addition of radicals and carbanions to ynol ethers. A strategy for the synthesis of exocyclic enol ethers. Tetrahedron 67, 92-99 (2011) [2].

(18) To a solution of ethoxyethyne (40 wt % in hexanes, 57 mmol, 1.25 equiv) in anhydrous THF (70 mL), n-BuLi (2.5 M, 63 mmol, 1.4 equiv) was added carefully at 78 C. After stirring for 1 h at 78 C., 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (15 mL, 126 mmol, 2.75 equiv) was added and the brown solution stirred for further 30 minutes at this temperature. After the careful addition of 1,3-diiodopropane (13.6 g, 46 mmol, 1.00 equiv) diluted in anhydrous THF (10 mL), the reaction mixture was allowed to warm to RT and stirred at this temperature for 20 h and at 50 C. for additional 2 h. The reaction was quenched with saturated ammonium chloride solution (90 mL), extracted with Et.sub.2O (3100 mL) and washed with brine (3100 mL). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and the solvent removed in vacuo. Purification by flash chromatography on silica with a gradient of n-heptane and EtOAc afforded the product (12.7 g, 48 mmol, 42% yield) as pale yellow oil.

(19) .sup.1H NMR (500 MHz, chloroform-d) 4.05 (q, 7.1 Hz, 2H), 3.32 (t, 6.8 Hz, 2H), 2.28 (t, 6.6 Hz, 2H), 1.95 (p, 6.7 Hz, 2H), 1.37 (t, 7.1 Hz, 3H).

(20) .sup.13C NMR (101 MHz, chloroform-d) 90.22, 77.48, 77.27, 77.16, 76.84, 74.15, 35.30, 33.17, 18.47, 14.50, 6.10.

1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene (2) (ethoxyethinyl Monomer), (E)

(21) ##STR00028##

(22) A suspension of 1-ethoxy-5-iodopent-1-yne (1) (3.00 g, 12.6 mmol, 1.00 equiv), freshly deprotected 4-vinylphenol (2.80 g, 23.3 mmol, 1.85 equiv), and K.sub.2CO.sub.3 (1.00 g, 7.0 mmol, 1.20 equiv) in anhydrous DMF (25 mL), was stirred for 20 hours at 50 C. After completion (judged by TLC) the reaction mixture was diluted with EtOAc (50 mL), washed with brine (550 mL) and dried over Na.sub.2SO.sub.4 and filtrated. The filtrate was adsorbed on silica and purification by flash chromatography on silica with a gradient of n-heptane and ethyl acetate afforded the product (2.42 g, 10.5 mmol, 83% yield) as colorless oil.

(23) .sup.1H NMR (500 MHz, chloroform-d) [ppm] 7.36-7.32 (m, 2H), 6.89-6.84 (m, 2H), 6.66 (dd, J=17.6, 10.9 Hz, 1H), 5.60 (dd, J=17.6, 1.0 Hz, 1H), 5.12 (dd, J 10.9, 0.9 Hz, 1H), 4.06 (t, J=6.3 Hz, 2H), 4.02 (q, J=7.1 Hz, 2H), 2.33 (t, J=6.9 Hz, 2H), 1.96-1.90 (m, 2H), 1.33 (t, J=7.1 Hz, 3H).

(24) .sup.13C NMR (101 MHz, chloroform-d) [ppm] 159.0, 136.4, 130.5, 127.5, 127.5, 114.7, 111.6, 89.9, 74.1, 66.7, 29.4, 14.5, 14.1.

3,6-dibutoxy-9H-carbazole (2)

(25) ##STR00029##

(26) At RT, 57 mL absolute 1-butanol (154 mmol, 10.0 eq) were dropwise added under stirring to a suspension 11.1 g NaH (460 mmol, 10.0 eq) in dry DMF. After gas release ceased, the mixture was stirred for an additional hour and the resulting sodium butanolate solution was then, under inert atmosphere, added to a suspension 35.0 g CuI (18.0 mmol, 4 eq) in 50 mL dry DMF. The reaction mixture has been stirred at 120 C. for 1 h, filtered through diatomaceous earth and evaporated with silica. Column elution with n-hexane/ethyl acetate gradient afforded, after eluate evaporation, the desired product as a white solid.

(27) Yield: 12.3 g (39.5 mmol, 86%)

(28) .sup.1H NMR (500 MHz; THF-ds) [ppm] 9.81 (s, 1H); 7.51 (d, J=2.4 Hz, 2H); 7.23 (dd, J=8.8 and 0.5 Hz, 2H); 6.94 (dd, J=8.7 and 2.4 Hz, 2H); 4.04 (t, J=6.5 Hz, 4H); 1.88-1.75 (m, 4H); 1.65-1.47 (m, 4H); 1.01 (t, J=7.4 Hz, 6H)

(29) .sup.13C NMR (126 MHz; chloroform-d) [ppm] 153.2; 135.4; 123.9; 115.9; 111.5; 104.1; 68.9; 31.74; 19.5; 14.1

4-(bis(4-(3,6-dibutoxy-9H-carbazol-9-yl)phenyl)amino) benzaldehyde (3)

(30) ##STR00030##

(31) 9.00 g 3,6-dibutoxy-9H-carbazole (2) (29.0 mmol, 2.4 eq), 6.30 g 4-(bis(4-iodophenyl)amino)benzaldehyde (29.0 mmol, 1.00 eq), 1.60 g copper bronze (25.0 mmol, 2.10 eq), 0.63 g [18]crown-6 (2.40 mmol, 0.20 eq) and 5.00 g K.sub.2CO.sub.3 (36.0 mmol, 3.00 eq) were stirred in 30 mL dry o-dichlorobenzene at 200 C. for 24 h. Then, the reaction mixture was diluted with 400 mL toluene, filtered through diatomaceous earth, the filtrate was three times washed with 100 mL brine, dried over sodium sulfate and vacuum evaporated to dryness. Recrystallization from toluene afforded the desired product as a yellowish solid.

(32) Yield: 9.00 g (10.1 mmol, 84%)

(33) .sup.1H NMR (500 MHz; THF-ds) [ppm] 9.86 (s, 1H); 7.85-7.77 (m, 2H); 7.66-7.60 (m, 8H); 7.57-7.49 (m, 4H); 7.38 (d, J=8.9 Hz, 4H); 7.32-7.26 (m, 2H); 7.00 (dd, J=8.9 and 2.4 Hz, 4H); 4.09 (t, J=6.5 Hz, 8H); 1.85-1.79 (m, 8H); 1.64-1.49 (m, 8H); 1.02 (t, J=7.4 Hz, 12H)

(34) .sup.13C NMR (126 MHz; CDCl.sub.3) [ppm] 190.6; 153.7; 153.1; 144.5; 136.2; 135.2; 131.7; 130.1; 127.9; 127.3; 123.9; 120.5; 115.9; 110.7; 104.1; 68.9; 31.7; 19.5; 14.1

4-(3,6-dibutoxy-9H-carbazol-9-yl)-N-(4-(3,6-dibutoxy-9H-carbazol-9-yl)phenyl)-N-(4-vinylphenyl)aniline (D)

(35) ##STR00031##

(36) A suspension 9.60 g methyl triphenyl phosphonium bromide (26.9 mmol, 3 eq) and 2.9 g potassium tert-butoxide (26.1 mmol, 2.90 eq) in dry 1,4-dioxane has been stirred for 2 h at 0 C., then, 8.00 g 4-(bis(4-(3,6-dibutoxy-9H-carbazol-9-yl)phenyl)amino)benzaldehyde (4) (8.97 mmol, 1.00 eq) were added in form of a solution in 200 mL dry toluene, while maintaining the temperature 0 C., the mixture has been stirred at this temperature for further 30 min., washed three times with 300 mL brine, dried over sodium sulfate, filtered and vacuum evaporated with silica. After column elution with n-heptane:toluene (1:2 v/v) and eluate evaporation, the desired product was obtained as a white solid.

(37) Yield: 7.23 g (8.12 mmol, 91%)

(38) .sup.1H NMR (500 MHz; THF-ds) [ppm] 7.64 (d, J=2.5 Hz, 4H); 7.56-7.46 (m, 10H); 7.46-7.41 (m, 4H); 7.36 (d; J=8.9 Hz, 4H); 7.31-7.27 (m, 4H); 7.02 (dd, J=8.9 and 2.4 Hz, 4H); 6.75 (dd, J=17.6 and 10.9 Hz, 1H); 5.75 (d, J=17.6 Hz, 1H); 5.19 (d, J=11.0 Hz, 1H); 4.10 (t, J=6.5 Hz, 8H); 1.87-1.82 (m, 8H); 1.62-1.54 (m, 8H); 1.04 (t, J=7.4 Hz, 12H)

(39) .sup.13C NMR (126 MHz, chloroform-d) [ppm] 153.4; 146.9; 146.0; 136.3; 133.0; 132.9; 129.0; 128.2; 127.6; 127.4; 124.9; 124.5; 123.5; 115.7; 110.6; 103.9; 68.8; 31.6; 19.4; 13.9

2-(perfluorophenyl)-7-(4-vinyl-[1,1-biphenyl]-3-yl)benzo[lmn][3,8]phenanthrolin-1,3,6,8(2H,7H)-tetraone (F)

7-(perfluorophenyl)-1H-isochromeno[6,5,4-def]isoquinoline-1,3,6,8(7H)-tetraone (LRT241)

(40) ##STR00032##

(41) To a suspension of naphthalene-1,4,5,8-tetracarboxylic dianhydride (6.43 g, 24 mmol) in DMF (150 mL) at 150 C. was added dropwise a solution of pentafluoroaniline (2.20 g, 12.00 mmol) in DMF (50 mL). Following addition, a clear dark-brown solution was obtained, which was further stirred at 150 C. for 5 hours until full consumption of pentafluoroaniline (determined by TLC). The reaction mixture was cooled down, and the reaction mixture was poured into water (500 mL). The resulting precipitate was recovered by filtration. The solid was dissolved in chloroform until a fine suspension is obtained. Filtration and concentration of the solution was followed by purification by silica-gel column chromatography using chloroform as eluent.

(42) Yield: 4.00 g, 76%.

(43) .sub.H (500 MHz, CDCl.sub.3): 8.92 (2H, d, J=7.5 Hz), 8.89 (2H, d, J=7.6 Hz).

2-(3-bromophenyl)-7-(perfluorophenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (LRT249)

(44) ##STR00033##

(45) To a solution of 7-(perfluorophenyl)-1H-isochromeno[6,5,4-def]isoquinoline-1,3,6,8(7H)-tetraone (4.00 g, 9.23 mmol) in DMF (50 mL) at 150 C., 3-bromoaniline (1 mL, 9.23 mmol) was added. The reaction was further heated at 150 C. overnight. Cooling down to room temperature was followed by addition of water (200 mL) and extraction with chloroform. The combined organic fractions were dried over MgSO.sub.4. After filtration and concentration the crude product was purified by silica-gel column chromatography using heptane/ethyl acetate (4:1) as eluent.

(46) Yield: 2.6 g, 47%.

(47) .sub.H (500 MHz, CDCl.sub.3): 8.93-8.85 (4H, m), 7.69 (1H, d, J=1.7 Hz), 7.53 (1H, s), 7.48 (1H, t, J=8.0 and 8.0 Hz), 7.31 (1H, d, J=6.1 Hz).

Synthesis of 2-(perfluorophenyl)-7-(4-vinyl-[1,1-biphenyl]-3-yl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (LRT255, (F))

(48) ##STR00034##

(49) 4-Vinylphenylboronic acid (0.65 g, 4.41 mmol), 2-(3-bromophenyl)-7-(perfluorophenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (2.00 g, 3.39 mmol), sodium carbonate (1.44 g, 13.6 mmol) and tetrakis(triphenyl-phosphine)palladium(0) (0.20 g, 0.17 mmol) were dissolved in a toluene/water (2:1) mixture (150 mL) and heated for 20 hours at 100 C. After completion of the reaction the reaction was cooled to room temperature. Phase separation was followed by extraction with dichloromethane. The combined organic phases were dried over MgSO.sub.4. The crude was purified on silica-gel column chromatography using toluene/acetone (95:5) as eluent. The product was recrystallized in methanol/dichloromethane mixtures.

(50) Yield: 1.60 g (77%).

(51) .sub.H (500 MHz, CDCl.sub.3): 8.89 (4H, d, J=6.6 Hz), 7.77 (1H, d, J=7.8 Hz), 7.66 (1H, t, J=7.8 and 7.8 Hz), 7.60 (2H, d, J=8.1 Hz), 7.56 (1H, s), 7.48 (2H, d, J=8.1 Hz), 7.32 (1H, d, J=7.7 Hz), 6.75 (1H, dd, J=17.6 and 10.9 Hz), 5.80 (1H, d, J=17.6 Hz), 5.29 (1H, d, J=10.9 Hz).

(52) Functional Polymers

poly[(N,N-bis(4-(9H-carbazole-9-yl)phenyl)-4-vinylaniline).SUB.55.-ran(1-(4-vinylphenyl)decane-1-one).SUB.30.-ran-(1-((5-ethoypent-4-yn-1-yl)oxy)-4-vinylbenzene).SUB.15.] FL241

(53) ##STR00035##

(54) 0.42 eq N,N-bis(4-(9H-carbazole-9-yl)phenyl)-4-vinylaniline (C), 0.40 eq 4-vinylphenyl decane and 0.25 eq 1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene (E) were stirred with 0.02 eq azo-bis(isobutyronitrile) (AIBN) in THF at overall mass concentration 0.1 g/mL for 72 h at 50 C., cooled to RT and the resulting polymer was precipitated from n-heptane:ethyl acetate 4:1 v/v mixture. The precipitate was collected using a PTFE filter (20 m porosity), dried dissolved in THF to a solution having mass concentration 0.05 g/mL and reprecipitated. After drying, the desired product was obtained as a white solid in 56% yield.

(55) .sup.1H NMR (500 MHz, chloroform-d) [ppm] 8.25-7.65 (aromatic), 7.45-5.90 (aromatic), 4.10-3.30 (alkoxy), 2.60-0.60 (backbone+aliphatic), resulting co-monomer ratio .sup.1H-NMR (m:n:o): 0.46:0.43:0.11, M.sub.w=38.5 kg mol.sup.1, M=19.0 kg mol.sup.1.

(56) Elemental analysis:

(57) Measured C, 86.63; H, 6.54; N, 5.26; O, 1.56

(58) Calculated (m=0.46, n=0.43, o=0.11): C, H, N, O

poly(N.SUP.1.-phenyl-N.SUP.4.-(4-(phenyl(m-tolyl)amino)phenyl)-N.SUP.1.-(m-tolyl)-N.SUP.4.-(4-vinylphenyl)benzene-1,4-diamine).SUB.79.-ran-(1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene).SUB.21.] FL262

(59) ##STR00036##

(60) N.sup.1-phenyl-N.sup.4-(4-(phenyl(m-tolyl)amino)phenyl)-N.sup.1-(m-tolyl)-N.sup.4-(4-vinylphenyl)benzene-1,4-diamine (0.66 eq) (B) and 0.33 eq 1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene (E) were stirred with 0.02 eq azo-bis(isobutyronitrile) (AIBN) in THF at overall mass concentration 0.1 g/mL for 72 h at 50 C., cooled to RT and the resulting polymer was precipitated from n-heptane:ethyl acetate 4:1 v/v mixture. The precipitate was collected using a PTFE filter (20 m porosity), dried dissolved in THF to a solution having mass concentration 0.05 g/mL and reprecipitated. After drying, the desired product was obtained as a white solid in 50% yield.

(61) .sup.1H NMR (500 MHz, chloroform-d) [ppm] 8.40-5.20 (aromatic), 4.00-3.40 (alkoxy), 2.40-0.80 (aliphatic+backbone), resulting co-monomer ratio .sup.1H-NMR (m:n): 0.79:0.21, M.sub.w=33.5 kg mol.sup.1, M.sub.n=18.9 kg mol.sup.1.

(62) Elemental analysis:

(63) Measured C, 86.39; H, 6.34; N, 6.07; O, 1.20

(64) Calculated (n=0.21): C, 86.38; H, 6.35; N, 6.05; O, 1.22

poly(N.SUP.4.-phenyl-N.SUP.4.,N.SUP.4.-d-m-tolyl-N.SUP.4.-(4-vinylpenyl)-[1,1-biphenyl]-4,4-diamine).SUB.76.-ran-(1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene).SUB.24.] FL253

(65) ##STR00037##

(66) 0.67 eq N.sup.4-phenyl-N.sup.4,N.sup.4-di-m-tolyl-N.sup.4-(4-vinylphenyl)-[1,1-biphenyl]-4,4-diamine (A) and 0.33 eq 1-((5-ethoxypent-4-in-1-yl)oxy)-4-vinylbenzene (E) were stirred with 0.02 eq azo-bis(isobutyronitrile) (AIBN) in THF at overall mass concentration 0.1 g/mL for 72 h at 50 C., cooled to RT and the resulting polymer was precipitated from n-heptane:ethyl acetate 4:1 v/v mixture. The precipitate was collected using a PTFE filter (20 m porosity), dried dissolved in THF to a solution having mass concentration 0.05 g/mL and reprecipitated. After drying, the desired product was obtained as a white solid in 57% yield.

(67) .sup.1H NMR (500 MHz, chloroform-d) [ppm] 7.40-6.20 (aromatic), 4.05-3.55 (alkoxy), 2.6-0.80 (aliphatic+backbone), resulting co-monomer ratio .sup.1H-NMR (m:n): 0.76:0.24, M.sub.w=28.0 kg mol.sup.1, M.sub.n=14.7 kg mol.sup.1.

(68) Elemental analysis:

(69) Measured C, 87.39; H, 6.55; N, 4.50; O, 1.79

(70) Calculated (n=0.24): C, 87.30; H, 6.50; N, 4.55; O, 1.64

poly[(4-(3,6-dibutoxy-9H-carbazol-9-yl)-N-(4-(3,6-dibutoxy-9H-carbazol-9-yl)phenyl)-N-(4-vinylphenyl)aniline).SUB.77.-ran-(1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene).SUB.23.] (FL272)

(71) ##STR00038##

(72) 0.67 eq 4-(3,6-dibutoxy-9H-carbazol-9-yl)-N-(4-(3,6-dibutoxy-9H-carbazol-9-yl)phenyl)-N-(4-vinylphenyl)aniline (D) (0.67 equiv) and 0.33 eq 1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene (E) were stirred with 0.02 eq azo-bis(isobutyronitrile) (AIBN) in toluene at overall mass concentration 0.1 g/mL for 72 h at 50 C., cooled to RT and the resulting polymer was precipitated from n-heptane:ethyl acetate 4:1 v/v mixture. The precipitate was collected using a PTFE filter (20 m porosity), dried dissolved in toluene to a solution having mass concentration 0.05 g/mL and reprecipitated. After drying, the desired product was obtained as a white solid in 68% yield.

(73) .sup.1H NMR (500 MHz, chloroform-d) [ppm] 7.85-6.15 (aromatic), 4.29-3.40 (alkoxy), 2.48-0.55 (aliphatic+backbone), monomer ratio (m:n): 0.76:0.24, M.sub.w=30.6 kg mol.sup.1, M.sub.n=16.7 kg mol.sup.1.

(74) Elemental analysis:

(75) Measured C, 80.43; H, 7.16; N, 4.35; O, 7.74

(76) Calculated (n=0.23): C, 80.76; H, 7.18; N, 4.38; O, 7.67

poly[(4-(3,6-dibutoxy-9H-carbazol-9-yl)-N-(4-(3,6-dibutoxy-9H-carbazol-9-yl)phenyl)-N-(4-vinylphenyl)aniline).SUB.65.-ran-(1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene).SUB.35.] (FL293)

(77) ##STR00039##

(78) 0.54 eq 4-(3,6-dibutoxy-9H-carbazol-9-yl)-N-(4-(3,6-dibutoxy-9H-carbazol-9-yl)phenyl)-N-(4-vinylphenyl)aniline (D) and 0.46 eq 1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene (E) were stirred with 20.02 eq azo-bis(isobutyronitrile) (AIBN) in toluene at overall mass concentration 0.1 g/mL for 144 h at 50 C., cooled to RT and the resulting polymer was precipitated from n-heptane:ethyl acetate 4:1 v/v mixture. The precipitate was collected using a PTFE filter (20 m porosity), dried dissolved in toluene to a solution having mass concentration 0.05 g/mL and reprecipitated. After drying, the desired product was obtained as a white solid in 68% yield. .sup.1H NMR (500 MHz, chloroform-d) [ppm] 7.85-6.15 (aromatic), 4.29-3.40 (alkoxy), 2.48-0.55 (aliphatic+backbone), monomer ratio (mm): 0.65:0.35, M, =26.5 kg mol.sup.1, M.sub.n=12.0 kg mol.sup.1.

(79) Elemental analysis:

(80) Measured C, 79.97; H, 7.34; N, 4.09, O 8.11

(81) Calculated (n=0.35): C, 80.63; H, 7.22; N, 4.14, O 8.01

poly[(4-(3,6-dibutoxy-9H-carbazol-9-yl)-N-(4-(3,6-dibutoxy-9H-carbazol-9-yl)phenyl)-N-(4-vinylphenyl)aniline).SUB.60.-ran-(1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene).SUB.40.] (FL298)

(82) ##STR00040##

(83) 0.50 eq 4-(3,6-dibutoxy-9H-carbazol-9-yl)-N-(4-(3,6-dibutoxy-9H-carbazol-9-yl)phenyl)-N-(4-vinylphenyl)aniline (D) and 0.50 eq 1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene (E) were stirred with 20.02 eq azo-bis(isobutyronitrile) (AIBN) in toluene at overall mass concentration 0.1 g/mL for 144 h at 50 C., cooled to RT and the resulting polymer was precipitated from n-heptane:ethyl acetate 4:1 v/v mixture. The precipitate was collected using a PTFE filter (20 m porosity), dried dissolved in toluene to a solution having mass concentration 0.05 g/mL and reprecipitated. After drying, the desired product was obtained as a white solid in 74% yield.

(84) .sup.1H NMR (500 MHz, chloroform-d) [ppm] 7.85-6.15 (aromatic), 4.29-3.40 (alkoxy), 2.48-0.55 (aliphatic+backbone), monomer ratio (m:n): 0.60:0.40, M.sub.w=22.7 kg mol.sup.1, M.sub.n=11.9 kg mol.sup.1,

(85) Elemental analysis:

(86) Measured C, 80.12; H, 7.27; N, 3.93; O, 8.32 Calculated (n=0.40): C, 80.56; H, 7.24; N, 4.03, O 8.18

poly[2-(perfluorophenyl)-7-(4-vinyl-[1,1-biphenyl]-3-yl)benzo[lmn][3,8]-phenanthroline-1,3,6,8(2H,7H)-tetraone-ran-1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene] (LRT269)

(87) ##STR00041##

(88) 2-(perfluorophenyl)-7-(4-vinyl-[1,1-biphenyl]-3-yl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (F) (0.40 g, 0.66 mmol) and 1-((5-ethoxypent-4-yn-1-yl)oxy)-4-vinylbenzene (E) (0.17 g, 0.75 mmol, 30 wt %) and AIBN (4.6 mg, 2 mol %) were dissolved in 5.8 mL (100 g/L concentration) of THF. The reaction was carried out in a glove box system under nitrogen atmosphere at 50 C. for 72 hours. A second amount of AIBN was added (9.6 mg, 4 mol %) and the reaction was heated at 50 C. for 72 hours. After cooling to room temperature the reaction was quenched with methanol. Unreacted monomer was separated by repeated precipitation of the prepared polymer in methanol, wherein the precipitated solid was separated from mother liquors, dissolved in tetrahydrofuran, filtered through syringe PTFE filter 0.2 m, the solution was concentrated and reprecipitated by pouring into methanol. The precipitate was filtered using PTFE membrane filters having pore size 0.45 m. The polymer was dried overnight at 50 C. in vacuum. Yield: 75 mg.

(89) The cross-linker content was estimated with DSC as 21.7 mol %; M.sub.w=4.05 kg mol.sup.1, M.sub.n=2.99 kg mol.sup.1. Conductivity and stability of a doped crosslinked layer

(90) 1) p-Doped Layer

(91) An anisole-acetonitrile 3:1 v/v solution containing 1.75% polymeric precursor FL253 and 0.44% p-dopant PR-7 was prepared and spin-coated on ITO substrate for 30 s at 1000 rpm. After drying and baking on hot plate in nitrogen atmosphere for 30 min at 180 C., conductivity and UV absorbance of the formed thin film at the wavelengths 340 nm (characteristic for charge transport structural moieties of the polymer) and 540 nm (characteristic absorption band of the active state of the p-dopant) were measured.

(92) The formed films were spin-rinsed with toluene after 10 s soaking-time before spinning. After 30 min drying at 80 C., the thickness and conductivity were measured again.

(93) The experiment has been repeated with C.sub.60F.sub.48 instead of PR-7 and with other exemplary precursor charge transport polymers. The results further amended with estimation of relative change in dopant absorbance after long-term illumination of the deposited layer with blue light are summarized in Table 2.

(94) TABLE-US-00002 TABLE 2 Material Dopant (weight ratio of Dopant Conductivity deteri- selected precursor wash- Polymer before/after oration by polymer and dopant out wash-off baking blue light given) % % 10.sup.6 S .Math. cm.sup.1 % FL253:PR-7 4:1 1 2.0 40/4 0.1 F253:C.sub.60F.sub.48 4:1 6 1.0 9/1 FL241:PR-7 4:1 6 1.0 2/ 1.0 FL272:PR-7 4:1 6 0.5 52/ 16 FL293:PR-7 4:1 12 2.0 22/ 0.4 FL298:PR-7 4:1 11 0.1 3/ 0.2

(95) 2) n-Doped Layer

(96) A toluene solution containing 2.0% polymeric precursor LRT269 and 0.2% n-dopant ND-1 was prepared and spin-coated on ITO substrate for 30 s at 1000 rpm. After drying 30 min at 60 C. and activation of the dopant by 1 h irradiation with UV light (366 nm), the conductivity was measured first time. Baking on hot plate in nitrogen atmosphere for 20 min at 160 C. followed, and conductivity was measured again. The conductivity after crosslinking was 1.10.sup.7 S.Math.cm.sup.1, whereas the value observed before baking was 4.10'S.Math.cm.sup.1.

(97) The rinsing test showed complete crosslinking of the doped layer. The experiment confirmed that thermal crosslinking of alkoxyacetylene structural moieties does not interfere with n-doping in the chosen model electron transporting polymer LRT269.

(98) Blue OLED

(99) On 90 nm thick indium tin oxide (ITO) layer fabricated on a glass substrate, 50 nm thick crosslinked hole-transporting layer from the tested precursor polymer FL272 doped with 20 wt. % PR-7 based on the overall polymer weight was cast by spin-coating from 2 wt. % anisole-acetonitrile solution. After drying and baking in an inert atmosphere at 180 C. for 40 minutes, a doped crosslinked layer having thickness 40 nm was obtained. Following layers were prepared on top of the crosslinked layer by vacuum deposition: 90 nm undoped electron blocking layer composed from N.sup.4,N.sup.4-di(naphtalen-1-yl)-N.sup.4,N.sup.4-diphenyl-[1,1:4,1-terphenyl]-4,4-diamine, 20 nm blue fluorescent emitting layer composed of ABH113 (obtained from Sun Fine Chem (SFC), Korea) doped with NUBD370 (also from SFC, host:emitter ratio 95:5 by weight), 30 nm electron transporting layer composed of 2-(4-(9,10-di(naphtalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (CAS 561064-11-7) and lithium 8-hydroxyquinolinolate (CAS 850918-68-2) in weight ratio 1:1 and 100 nm thick Al cathode. At current density 15 mA/cm, the OLED prepared using the precursor polymer FL272 had, despite 2 h baking of the HTL, operational voltage 4.6 V and -quantum efficiency 5.2%. The lifetime of the OLED, expressed as LT97 (the time necessary for luminance decrease to 97% of its initial value), was 60 hours. The results, together with results of experiments with shorter baking time and with precursor polymer FL253, are summarized in Table 3.

(100) TABLE-US-00003 TABLE 3 material/ V Qeff LT97 baking @15 @15 @15 duration mA/cm.sup.2 mA/cm.sup.2 mA/cm.sup.2 Operational (min) (V) (%) CiEy h stability FL272:PR-7 4.7 5.2 0.10 50 yes 4:1 40 FL272:PR-7 4.6 5.2 0.10 66 yes 4:1 120 FL253:PR-7 4.9 5.6 0.10 30 yes 4:1 40 FL253:PR-7 5.5 5.7 0.10 30 yes 4:1 120

(101) FIGS. 1 and 2 show current-voltage characteristics and lifetime of blue OLEDs prepared as described in Example, using baking time 40 minutes; curve (1), (circles), corresponds the OLED of the first row of the Table 3, curve (2), (stars) corresponds the third row.

(102) The results summarized in Table 2 show that the conductivity of 10.sup.6-10.sup.5 S/cm, as required for a hole transporting layer, was maintained in the doped layer after cross-linking. If the dopant was destroyed during the cycloaddition reaction, a significantly lower conductivity of about 10.sup.10 S/cm would be obtained.

(103) The OLED experiments summarized in Table 3 confirmed robustness of the inventive doped material, wherein efficiency and/or device-lifetime can be further increased by prolonged heat treatment of the doped layer, without a substantial change in spectral characteristics of the device (represented by the CIEy value which stands for y coordinate in colour space according to International Commission on Illumination) and without a substantial increase in operational voltage.

(104) The results demonstrate that crosslinked charge transporting layers comprising semi-conducting material according to the invention can be successfully used in organic electronic devices.

(105) The features disclosed in the foregoing description may, both separately and in any combination thereof, be material for realizing various embodiments of the invention which is generically defined in the independent claims.