Hole transporting organic molecules containing enamine groups for optoelectronic and photoelectrochemical devices

Abstract

The present invention relates to a compound of formula (I) based on enamine derivatives and used as organic hole conductors or hole transporting material in an optoelectronic or photoelectrochemical device. The present invention relates to the hole transporting compounds based on enamine derivatives for efficiency perovskite or dye sensitized solar cells and optoelectronic devices, organic light-emitting diode (OLED), field-effect transistors (FET).

Claims

1. A compound of formula (I): ##STR00055## wherein n is 1, 2, 3, 4, 5, 6, 7 or 8; Q is a mono- or polycyclic system comprising at least one pair of a conjugated double bond (—C═C—C═C—), the polycyclic system comprising fused aromatic rings or monocyclic aromatic rings bound together by covalent bond or heteroaromatic system with N, O, S, Se, Si heteroatoms; wherein said mono- or polycyclic system being substituted by H, halogen, cyano group, C1-C20 cyanoalkyl group, C1-C20 alkyl, C1-C20 alkoxy group, C1-C20 alkoxyalkyl, C1-C20 haloalkyl group, C1-C20 haloalkoxyalkyl, wherein said cyanoalkyl, alkyl, alkoxy, alkoxyalkyl, haloalkyl, haloalkoxyalkyl, C4-C20 aryl, C4-C20 alkylaryl, C4-C20 alkoxyaryl, C4-C20 alkenylarylalkyl, C4-C20 alkoxyarylalkenyl, C4-C20 bisalkoxyarylalkenylo groups if the groups comprise 3 or more carbons, the groups are linear, branched or cyclic, wherein halogen is selected from Cl, F, Br, or I; R is a substituent, on each occurrence, identically or differently selected from C1-C20 alkyl, C2-C20 alkenyl, C4-C20 arylalkenyl, C4-C20 aryl groups, wherein said aryl and arylalkenyl groups are unsubstituted or substituted with C1-C20 alkyl or C1-C20 alkoxy groups, if the groups comprise 3 or more carbons, the groups are linear, branched or cyclic; R.sup.1, R.sup.2, R.sup.3, R.sup.4 are independent one from another and selected from hydrogen, halogen, cyano, C1-C20 cyanoalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkoxyalkyl, C1-C20 haloalkyl, C1-C20 haloalkoxyalkyl groups, if the groups comprise 3 or more carbons, the groups are linear, branched or cyclic, wherein halogen is selected from Cl, F, Br, or wherein the compound of formula (I) is selected from any one of compounds: 9-ethyl-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (1); 9-butyl-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (2); 9-hexyl-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (3); 9-(2-ethylhexyl)-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (4); 9-butyl-6-(-butyl)-3-{N,N-[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (5); 4-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}triphenylamine (6); 9-butyl-3,6-bis{N.sup.3,N.sup.3,N.sup.6,N.sup.6-tetrakis(2,2-bis[4-methoxyphenyl)vinyl]amino}-9H-carbazole (7); 9-(2-ethylhexyl)-3,6-bis{N.sup.3,N.sup.3,N.sup.6,N.sup.6-tetrakis(2,2-bis[4-methoxyphenyl)vinyl]-amino}-9H-carbazole (8); N.sup.3,N.sup.3,N.sup.6,N.sup.6,9-pentakis(2,2-bis(4-methoxyphenyl)vinyl)-9H-carbazole-3,6-diamine (9); N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9H-fluorene-2,7-diamine (10); N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9-dimethyl-9H-fluorene-2,7-diamine (11); N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9-dipropyl-9H-fluorene-2,7-diamine (12); N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9-dihexyl-9H-fluorene-2,7-diamine (13); 9,9-dibenzyl-N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9H-fluorene-2,7-diamine (14); N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluoren]-2-amine (15); N.sup.2,N.sup.2,N.sup.2′,N.sup.2′-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluorene]-2,2′-diamine (16); N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluorene]-2,7-diamine (17); N.sup.2,N.sup.2,N.sup.2′,N.sup.2′,N.sup.7,N.sup.7,N.sup.7′,N.sup.7′-octakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluorene]-2,2′,7,7′-tetraamine (18).

2. The compound of formula (I) according to claim 1 for use in a photovoltaic device as nonpolymeric hole transporting materials.

3. The hole transporting material comprising at least one small molecule hole transporting material being selected from one of compounds of formula (I) according to claim 2.

4. The photovoltaic device comprising a compound of formula (I) according to claim 2.

5. A hole transporting material comprising at least one small molecule hole transporting material being selected from one of compounds of formula (I) according to claim 1.

6. A method of using a compound according to claim 1 as a hole transporting material in photovoltaic device.

7. The compound of the formula (I) according to claim 1 for use in photovoltaic device as nonpolymeric hole transporting materials.

8. The hole transporting material comprising at least one small molecule hole transporting material being selected from one of compounds of formula (I) according to claim 7.

9. The photovoltaic device comprising a compound of formula (I) according to claim 7.

10. The hole transporting material comprising at least one small molecule hole transporting material being selected from one of compounds of formula (I) according to claim 1.

11. The photovoltaic device comprising a compound of formula (I) according to claim 1.

12. A photovoltaic device comprising a compound of formula (I), wherein the compound is selected from any one of compounds: 9-ethyl-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (1); 9-butyl-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (2); 9-hexyl-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (3); 9-(2-ethylhexyl)-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (4); 9-butyl-6-(-butyl)-3-{N,N-[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (5); 4-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}triphenylamine (6); 9-butyl-3,6-bis{N.sup.3,N.sup.3,N.sup.6,N.sup.6-tetrakis(2,2bis[4-methoxyphenyl)vinyl]amino}-9H-carbazole (7); 9-(2-ethylhexyl)-3,6-bis{N.sup.3,N.sup.3,N.sup.6,N.sup.6-tetrakis(2,2-bis[4-methoxyphenyl)vinyl]-amino}-9H-carbazole (8); N.sup.3,N.sup.3,N.sup.6,N.sup.6,9-pentakis(2,2-bis(4-methoxyphenyl)vinyl)-9H-carbazole-3,6-diamine (9); N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9H-fluorene-2,7-diamine (10); N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9-dimethyl-9H-fluorene-2,7-diamine (11); N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9-dipropyl-9H-fluorene-2,7-diamine (12); N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9-dihexyl-9H-fluorene-2,7-diamine (13); 9,9-dibenzyl-N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9H-fluorene-2,7-diamine (14); N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluoren]-2-amine (15); N.sup.2,N.sup.2,N.sup.2′,N.sup.2′-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluorene]-2,2′-diamine (16); N.sup.2,N.sup.2,N.sup.7,N.sup.7-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluorene]-2,7-diamine (17); N.sup.2,N.sup.2,N.sup.2′,N.sup.2′,N.sup.7,N.sup.7,N.sup.7′,N.sup.7′-octakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluorene]-2,2′,7,7′-tetraamine (18).

13. The photovoltaic device according to claim 12, comprising a hole transporting material, wherein said hole transporting material comprises the compound of formula (I).

14. The photovoltaic device according to claim 13 which is a solid state solar cell comprising an organic-inorganic perovskite as sensitizer under the form of a layer.

15. The photovoltaic device according to claim 14, wherein the organic-inorganic perovskite layer material comprises a perovskite-structure of formula (II):
AMX.sub.3  (II) wherein A is an alkali metal ion, wherein one or more hydrogens are substituted by alkyl or acyl group, wherein said-ammonium ions, include mono, di, tri and tetra alkyl ammonium ions, wherein one or more hydrogens are substituted by alkyl group, wherein said ammonium ions, include amidinium, N-alkyl amidinium and imidinium ions, wherein one or more hydrogens are substituted by alkyl group, wherein the hydrogen atoms in the organic cations A are substituted by halogens selected from the group consisting of F, Cl, I and Br, M is a divalent metal cation selected from the group consisting of Cu.sup.2+, Ni.sup.2+, Co.sup.2+, Fe.sup.2+, Mn.sup.2+,Cr.sup.2+, Pd.sup.2+, Cd.sup.2+, Ge.sup.2+, Sn.sup.2+, Pb.sup.2+, EU.sup.2+, or Yb.sup.2+; and X is monovalent anion, independently selected from the group consisting of Cl.sup.−, Br.sup.−, I, NCS.sup.−, CN.sup.−, and NCO.sup.−.

16. The photovoltaic device according to claim 15, wherein the organic-inorganic perovskite layer material comprises a perovskite-structure of formula (II):
AMX.sub.3  (II) wherein A is an alkali metal ion, is Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+; ammonium or formamidium ion, wherein one or more hydrogens are substituted by alkyl or acyl group, wherein-said ammonium ions, include mono, di, tri and tetra alkyl ammonium ions, wherein one or more hydrogens are substituted by alkyl group, the substituent is alkyl group or groups independently selected from C1-C6, is methyl or ethyl groups, wherein said ammonium ions, include amidinium, N-alkyl amidinium and imidinium ions, wherein one or more hydrogens are substituted by alkyl group, the amidinium or imidinium ions are selected from C1-C6 carboxamide groups, formamidium or acetamidium groups, wherein the hydrogen atoms in the organic cations A may be substituted by halogens selected from the group consisting of F, Cl, I and Br, are-F or Cl; A is Cs.sup.+ or methyl ammonium ion (MA.sup.+), or formamidium ion (FA.sup.+); M is a divalent metal cation selected from the group consisting of Cu.sup.2+, Ni.sup.2+, Co.sup.2+, Fe.sup.2+, Mn.sup.2+,Cr.sup.2+, Pd.sup.2+, Cd.sup.2+, Ge.sup.2+, Sn.sup.2+, Pb.sup.2+, EU.sup.2+, or Yb.sup.2+; are Pb.sup.2+, Sn.sup.2+; and X is monovalent anion, independently selected from the group consisting of Cl.sup.−, Br.sup.−, I, NCS.sup.−, CN.sup.−, and NCO.sup.−; are Cl.sup.−, Br.sup.−, I.sup.−.

17. The photovoltaic device according to claim 14, wherein the organic-inorganic perovskite layer material comprises a mixed perovskite-structure of the formulae (III) below:
A.sup.1.sub.1-yA.sup.2.sub.yPbX.sup.1.sub.3-zX.sup.2.sub.z  (III) wherein: A.sup.1 and A.sup.2 are organic monovalent cations as defined for A, wherein A is an alkali metal ion, wherein one or more hydrogens are substituted by alkyl or acyl group, wherein said ammonium ions, include mono, di, tri and tetra alkyl ammonium ions, wherein one or more hydrogens are substituted by alkyl group, wherein said ammonium ions, include amidinium, N-alkyl amidinium and imidinium ions, wherein one or more hydrogens are substituted by alkyl group, wherein the hydrogen atoms in the organic cations A are substituted by halogens selected from the group consisting of F, Cl, I and Br; X.sup.1 and X.sup.2 are the same or different monovalent anions selected from the group consisting of Cl.sup.−, Br.sup.−, I.sup.−, NCS.sup.−, CN.sup.− and NCO.sup.−; y is in the interval between 0.1 and 0.9; and z is in the interval between 0.2 and 2.

18. The photovoltaic device according to claim 17, wherein the organic-inorganic perovskite layer material comprises a mixed perovskite-structure of the formulae (III) below:
A.sup.1.sub.1-yA.sup.2.sub.yPbX.sup.1.sub.3-zX.sup.2z  (III) wherein: A.sup.1 and A.sup.2 are organic monovalent cations as defined for A, wherein: A is an alkali metal ion, is Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+; ammonium or formamidium ion, wherein one or more hydrogens are substituted by alkyl or acyl group, wherein-said ammonium ions, include mono, di, tri and tetra alkyl ammonium ions, wherein one or more hydrogens are substituted by alkyl group, the substituent is alkyl group or groups independently selected from C1-C6, is methyl or ethyl groups, wherein said ammonium ions, include amidinium, N-alkyl amidinium and imidinium ions, wherein one or more hydrogens are substituted by alkyl group, the amidinium or imidinium ions are selected from C1-C6 carboxamide groups, are formamidium or acetamidium groups, wherein the hydrogen atoms in the organic cations A are substituted by halogens selected from the group consisting of F, Cl, I and Br, are-F or Cl; A is Cs.sup.+ or methyl ammonium ion (MA.sup.+), or formamidium ion (FA.sup.+); M is a divalent metal cation selected from the group consisting of Cu.sup.2+, Ni.sup.2+, Co.sup.2+, Fe.sup.2+, Mn.sup.2+,Cr.sup.2+, Pd.sup.2+, Cd.sup.2+, Ge.sup.2+, Sn.sup.2+, Pb.sup.2+, EU.sup.2+, or Yb.sup.2+; are Pb.sup.2+, Sn.sup.2+; and X is monovalent anion, independently selected from the group consisting of Cl.sup.−, Br.sup.−, I, NCS.sup.−, CN.sup.−, and NCO.sup.−; are Cl.sup.−, Br.sup.−, I.sup.−: X.sup.1 and X.sup.2 are the same or different monovalent anions selected from the group consisting of Cl.sup.−, Br.sup.−, I.sup.−, NCS.sup.−, CN.sup.− and NCO.sup.−; y is in the interval between 0.1 and 0.9; and z is in the interval between 0.2 and 2.

19. The photovoltaic device according to claim 13, which is a solid state solar cell comprising an organic-inorganic perovskite as sensitizer under the form of a layer and coated by the compound of formula (I) ##STR00056## under the form of a layer.

20. The photovoltaic device according to claim 13 which is selected from an organic photovoltaic device, a photovoltaic solid state device, an p-n heterojunction, an organic solar cell, a dye sensitized solar cell, and solid state solar cell.

21. The photovoltaic device according to claim 12 which is selected from an organic photovoltaic device, a photovoltaic solid state device, an pn heterojunction, an organic solar cell, a dye sensitized solar cell, and solid state solar cell.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the Current-Voltage curve of solar cells where compound (1) corresponding to compound V-950 and Spiro-OMeTAD are explored as hole transporting materials.

(2) FIG. 2 shows the incident photon to current efficiency (IPCE) curve of solar cells where compound (1) corresponding to compound V-950 and Spiro-OMeTAD are explored as hole transporting materials.

DETAILED DESCRIPTION OF THE INVENTION

(3) General Synthesis Scheme of Compounds of General Formula (I).

(4) Hole transporting compounds containing enamine groups (—N—C═C) corresponding to the general formula (I) were synthesized via condensation reaction between 2,2-bis(4-methoxyphenyl)acetaldehyde (T. Kodera, K. Torizuka (Mitsubishi Paper Mills, Ltd.), Jpn. Kokai Tokkyo Koho JP 11043458, 1999) and primary, 3-amino-9-ethyl-9H-carbazole (Sigma-Aldrich), for example, or secondary amine of heterocycle in the presence of the catalyst (+/−) 10-camphorsulfonic acid (CSA) at reflux of toluene (FIG. 1). Dean-Stark apparatus is used to shorten reaction time and this is the main difference of the above mentioned method from the one described in the literature (Synthetic Metals, Vol. 158, 2008, 993). Compounds 1-5 were synthesized according to this method (Scheme 1):

(5) ##STR00013##

(6) Hole transporting compound 6 containing enamine groups and corresponding to the general formula (I) was synthesized via condensation between 2,2-bis(4-methoxyphenyl)acetaldehyde and aromatic amine, 4-aminotriphenylamine (TCI Europe N.V.), for example, in the presence of the catalyst (+/−)10-camphorsulfonic acid (CSA) and using Dean-Stark apparatus (Scheme 2):

(7) ##STR00014##

(8) It is well-know that increase in the size of the 7r-conjugated system results in better charge transporting properties, therefore; in addition to the mono enamines 1-6, dienamines 7, 8, and 9 with enlarged π-conjugated system, were also synthesized from 3,6-diamino-9H-butylcarbazole, 3,6-diamino-9H-(2-ethylhexyl)carbazole, 3,6-diamino-9H-carbazole and, i.e., from the 9H-carbazoles, possessing several amino groups Scheme 3).

(9) ##STR00015##

(10) Hole transporting fluorene-based compounds 10-14 containing enamine groups and corresponding to the general formula (I) were synthesized using straightforward chemistry with excellent yields and high purity. As shown in Scheme 4, hole transporting material 10 only required one-pot reaction condensing inexpensive commercially available 2,7-diaminofluorene (TC Europe N.V.) and 2,2-bis(4-methoxyphenyl)acetaldehyde in the presence of camphor sulfonic acid. Compound 10 was further reacted with different alkylating agents (RX) in the presence of interphase catalyst benzyltriethylammonium chloride (BTEAC) to yield methyl-, propyl-, hexyl-, and benzyl-substituted fluorene enamines as final HTMs 11, 12, 13, and 14, respectively.

(11) ##STR00016##

(12) Hole transporting spirofluorene-based compounds 15-18 containing enamine groups and corresponding to the general formula (I) were synthesized in one-pot reaction condensing commercially available 9,9′-spirobi[9H-fluoren]-2-amine (TC Europe N.V.), 9,9′-spirobi[fluorene]-2,7-diamine (Fluorochem Ltd), 2,2′,7,7′-tetraamino-9,9′-spirobifluorene (ABClabtory Scientific Co., Ltd.), and 9,9′-spirobi[fluorene]-2,7-diamine with (2,2-bis(4-methoxyphenyl)acetaldehyde in the presence of camphor sulfonic acid (Scheme 5).

(13) ##STR00017##

MODES FOR CARRYING OUT THE INVENTION

(14) Information on examples of real embodiments is provided below, describing the modes of preparation compounds (1-18) of present invention and properties thereof. This information is provided for the illustrative purpose and is not limiting the scope of the present invention.

Example 1

9-ethyl-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (see Scheme 1, Compound I or V-950)

(15) ##STR00018##

(16) 3-amino-9-ethylcarbazole (250 mg, 1.19 mmol) is dissolved in toluene (5 ml+volume of Dean-Stark apparatus), (+/−)10-camphorsulfonic acid (276 mg, 1.19 mmol) was added and reaction mixture was refluxed for 20 min. Then 2,2-bis(4-methoxyphenyl)acetaldehyde (915 mg, 3.57 mmol) was added and reaction was continued using Dean-Stark apparatus for another 2 hours. After reaction was finished (TLC, acetone:n-hexane/v:v, 1:4) reaction mixture was extracted with ethyl acetate, organic layer dried with anhydrous Na.sub.2SO.sub.4, filtered and organic solvents removed in vacuum. The residue was dissolved in warm ethanol; formed crystals were filtered, washed with cold ethanol and recrystallized from the mixture of toluene:ethanol (1:2). Obtained crystals were dried under vacuum at 40° C. to yield 1 as yellow crystals (590 mg, 64 10%); m.p. 226-228° C.

(17) .sup.1H NMR (700 MHz, DMSO-d.sub.6, δ): 8.15 (d, J=7.8 Hz, 1H, 5-H, Ht), 7.80 (s, 1H, 4-H, Ht), 7.58-7.54 (m, 2H, 1,2-H, Ht), 7.44-7.40 (m, 1H 6-H, Ht), 7.24 (d, J=7.0 Hz, 1H, 8-H, Ht), 7.11-7.08 (m, 1H, 7-H, Ht), 6.96 (d, J=8.8 Hz, 4H, p-Ph), 6.88 (d, J=9.0 Hz, 4H, p-Ph), 6.67 (d, J=9.0 Hz, 4H, p-Ph), 6.44 (d, J=8.8 Hz, 4H, p-Ph), 5.79 (s, 2H, NCH), 4.42 (kv, J=7.0 Hz, 2H, NCH.sub.2), 3.79 (s, 6H, OCH.sub.3), 3.70 (s, 6H, OCH.sub.3), 1.31 (t, J=7.0 Hz, 3H, CH.sub.3).

(18) .sup.13C NMR (176 MHz, DMSO-d.sub.6 6): 159.1, 139.1, 136.4, 134.5, 132.6, 132.3, 130.7, 129.3, 128.7, 127.6, 126.3, 123.43, 122.33, 121.37, 118.76, 117.16, 114.35, 114.24, 113.53, 110.14, 109.47, 108.72, 55.1 (OCH.sub.3), 55.51 (OCH.sub.3), 37.46 (CH.sub.2), 14.15 (CH.sub.3).

(19) Elemental analysis: Calculated, %: C, 80.44; H, 6.16; N, 4.08. C.sub.46H.sub.42N.sub.2O.sub.4. Found, %: C, 80.17; H, 6.02; N, 3.91.

Example 2

9-butyl-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (see Scheme 1, Compound 2 or V-1013)

(20) ##STR00019##

(21) 3-amino-9-butylcarbazole (1 g, 4.2 mmol) is dissolved in toluene (18 ml), (+/−)10-camphorsulfonic acid (1 g, 4.3 mmol) was added and reaction mixture was refluxed for 20 min. Then 2,2-bis(4-methoxyphenyl)acetaldehyde (2.69 g, 10.5 mmol) was added and reaction was continued using Dean-Stark apparatus for another 1 hour. After reaction was finished (TLC, acetone:n-hexane/v:v, 1:4) reaction mixture was extracted with ethyl acetate, organic layer dried with anhydrous Na.sub.2SO.sub.4, filtered and organic solvents removed in vacuum. The residue was purified by column chromatography using THF: n-hexane/v:v, 1:49 and recrystallized from ethanol. Obtained crystals were dried under vacuum at 40° C. to yield 2 as yellow crystals (1.65 g, 55%).

(22) .sup.1H NMR (400 MHz, CDCl.sub.3 δ): 8.05 (d, J=8.9 Hz, 1H, 5-H, Ht), 7.81 (s, 1H, 4-H, Ht), 7.44 (t, J=7.2 Hz, 1H, 6-H, Ht), 7.39-7.33 (m, 1H, 8-H, Ht), 7.33 (t, J=7.5 Hz, 2H, 1,2-H, Ht), 7.17 (t, J=7.4 Hz, 1H, 7-H, Ht), 7.07 (d, J=8.7 Hz, 4H, p-Ph), 6.83 (d, J=8.7 Hz, 4H, p-Ph), 6.67 (d, J=8.7 Hz, 8 Hz, 4H, p-Ph), 6.54 (d, J=8.7 Hz, 4H, p-Ph), 5.89 (s, 2H, NCH), 4.30 (t, J=7.2 Hz, 2H, NCH.sub.2), 3.85 (s, 6H, OCH.sub.3), 3.77 (s, 6H, OCH.sub.3), 1.88-1.82 (m, 2H, NCH.sub.2), 1.55 (s, 2H, NCH.sub.2CH.sub.2), 1.44-1.39 (m, 2H, NCH.sub.2CH.sub.2CH.sub.2), 0.96 (t, J=7.2 Hz, 3H, CH.sub.3).

(23) .sup.13C NMR (75 MHz, CDCl.sub.3 δ): 159.0, 158.7, 141.2, 139.2, 136.9, 134.9, 133.2, 130.8, 129.8, 128.9, 127.9, 125.9, 123.7, 122.6, 120.9, 118.5, 116.9, 114.6, 114, 113.2, 109.1, 108.8, 55.6 (OCH.sub.3), 55.4 (OCH.sub.3), 43.1 (CH.sub.2), 31.4 (CH.sub.2), 20.7 (CH.sub.2), 14.1 (CH.sub.3).

(24) Elemental analysis: Calculated, %: C, 80.64; H, 6.49; N, 3.92. C.sub.48H.sub.46N.sub.2O.sub.4. Found, %: C, 80.44; H, 6.29; N, 3.72.

Example 3

9-hexyl-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (see Scheme 1, Compound 3 or V-1001)

(25) ##STR00020##

(26) 3-amino-9-hexylcarbazole (1 g, 3.8 mmol) is dissolved in toluene (18 ml), (+/−)10-camphorsulfonic acid (1 g, 4.3 mmol) was added and reaction mixture was refluxed for 20 min. Then 2,2-bis(4-methoxyphenyl)acetaldehyde (2.41 g, 9.4 mmol) was added and reaction was continued using Dean-Stark apparatus for another 1 hour. After reaction was finished (TLC, acetone:n-hexane/v:v, 1:4) reaction mixture was extracted with ethyl acetate, organic layer dried with anhydrous Na.sub.2SO.sub.4, filtered and organic solvents removed in vacuum. The residue was purified by column chromatography using acetone: n-hexane/v:v, 1:49 and recrystallized from ethanol. Obtained crystals were dried under vacuum at 40° C. to yield 3 as yellow crystals (1.56 g, 55%).

(27) .sup.1H NMR (400 MHz, CDCl.sub.3 δ): 8.07 (d, J=7.7 Hz, 1H, 5-H, Ht), 7.8 (s, 1H, 4-H, Ht), 7.38 (d, 1H, J=8.2 Hz, 1H, 7-H, Ht), 7.33 (t, J=3.6 Hz, 2H, 6-H, Ht), 7.12-7.19 (m, 1H, 8-H, Ht), 7.07 (t, J=5.7 Hz, 4H, p-Ph), 6.84 (t, J=5.8 Hz, 4H, p-Ph), 6.65-6.68 (m, 4H, p-Ph), 6.53-6.56 (m, 4H, p-Ph), 5.89 (s, 2H, NCH), 4.8 (t, J=7.2 Hz, 2H, NCH.sub.2), 3.84 (s, 6H, OCH.sub.3), 3.77 (s, 6H, OCH.sub.3), 1.85-1.89 (m, 2H, NCH.sub.2CH.sub.2), 1.37-1.41 (m, 2H, NCH.sub.2CH.sub.2CH.sub.2), 1.29-1.33 (m, 4H, NCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2), 0.88 (t, J=7.0 Hz, 3H, CH.sub.3).

(28) .sup.13C NMR (100 MHz, CDCl.sub.3 δ): 159.0, 158.7, 141.2, 139.2, 136.2, 134.9, 133.2, 130.8, 129.8, 128.9, 127.9, 125.9, 123.7, 122.6, 120.9, 118.6, 116.9, 114.6, 114.0, 113.2, 109.1, 108.7, 55.6 (OCH.sub.3), 55.4 (OCH.sub.3), 43.4 (CH.sub.2), 31.8 (CH.sub.2), 29.1 (CH.sub.2), 27.1 (CH.sub.2), 22.7 (CH.sub.2), 14.2 (CH.sub.3).

(29) Elemental analysis: Calculated, %: C, 80.83; H, 6.78; N, 3.77. C.sub.50H.sub.50N.sub.2O.sub.4. Found, %: C, 80.63; H, 6.68; N, 3.57.

Example 4

9-(2-ethylhexyl)-3-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (see Scheme 1, Compound 4 or V-1000)

(30) ##STR00021##

(31) 3-amino-9-(2-ethylhexyl)carbazole (1 g, 3.4 mmol) is dissolved in toluene (17 ml), (+/−) 10-camphorsulfonic acid (1 g, 4.3 mmol) was added and reaction mixture was refluxed for 20 min. Then 2,2-bis(4-methoxyphenyl)acetaldehyde (2.18 g, 8.5 mmol) was added and reaction was continued using Dean-Stark apparatus for another 1 hour. After reaction was finished (TLC, acetone:n-hexane/v:v, 1:4) reaction mixture was extracted with ethyl acetate, organic layer dried with anhydrous Na.sub.2SO.sub.4, filtered and organic solvents removed in vacuum. The residue was purified by column chromatography using acetone: n-hexane/v:v, 1:49 and recrystallized from ethanol. Obtained crystals were dried under vacuum at 40° C. to yield 4 as yellow crystals (1.45 g, 57%).

(32) .sup.1H NMR (400 MHz, CDCl.sub.3 δ): 8.06 (d, J=7.8 Hz, 1H, 5-H, Ht), 7.81 (s, 1H, 4-H, Ht), 7.7 (t, J=7.7 Hz, 1H, 6-H, Ht), 7.36-7.34 (m, 1H, 8-H, Ht), 7.33-7.31 (m, 2H, 1,2-H, Ht), 7.17 (t, J=7.4 Hz, 1H, 7-H, Ht), 7.07 (d, J=8.4 Hz, 4H, p-Ph), 6.84 (d, J=8.4 Hz, 4H, p-Ph), 6.67 (d, J=8.4 Hz, 4H, p-Ph), 6.54 (d, J=8.4 Hz, 4H, p-Ph), 5.89 (s, 2H, NCH), 4.18-4.11 (m, 2H, NCH.sub.2), 3.85 (s, 6H, OCH.sub.3), 3.77 (s, 6H, OCH.sub.3), 2.08-2.05 (m, 1H, NCH.sub.2CH), 1.44-1.32 (m, 6H, NCH.sub.2(CH.sub.2)3), 1.32-1.27 (m, 2H, NCH.sub.2CHCH.sub.2), 0.93 (t, J=7.3 Hz, 3H, CH.sub.2CH.sub.3), 0.89 (t, J=7.3 Hz, 3H, CH.sub.2CH.sub.3).

(33) .sup.13C NMR (100 MHz, CDCl.sub.3, δ): 159.0, 158.7, 141.7, 139.2, 137.4, 134.9, 133.2, 130.8, 129.8, 128.9, 127.9, 125.8, 123.6, 122.6, 120.9, 118.6, 116.9, 114.6, 114.0, 113.2, 109.4, 109.1, 108.7, 55.6 (OCH.sub.3), 55.4 (OCH.sub.3), 47.7 (CH), 39.7 (CH.sub.2), 31.2 (CH.sub.2), 29.0 (CH.sub.2), 24.5 (CH.sub.2), 23.2 (CH.sub.2), 14.2 (CH.sub.3), 11.1 (CH.sub.3).

(34) Elemental analysis: Calculated, %: C, 81.01; H, 7.06; N, 3.63. C.sub.52H.sub.54N.sub.2O.sub.4. Found, %: C, 80.81; H, 6.84; N, 3.43.

Example 5

9-butyl-6-(tert-butyl)-3-{N,N-[2,2-bis(4-methoxyphenyl)vinyl]amino}-9H-carbazole (see Scheme 1, Compound 5 or V-1004)

(35) ##STR00022##

(36) 3-amino-6-(tert-butyl)-9-butylcarbazole (1 g, 3.4 mmol) is dissolved in toluene (17 ml), (+/−)10-camphorsulfonic acid (1 g, 4.3 mmol) was added and reaction mixture was refluxed for 20 min. Then 2,2-bis(4-methoxyphenyl)acetaldehyde (2.18 g, 8.5 mmol) was added and reaction was continued using Dean-Stark apparatus for another 30 min. After reaction was finished (TLC, acetone:n-hexane/v:v, 1:4) reaction mixture was extracted with ethyl acetate, organic layer dried with anhydrous Na.sub.2SO.sub.4, filtered and organic solvents removed in vacuum. The residue was purified by column chromatography using THF: n-hexane/v:v, 1:24 and precipitated from 20% solution in THF to 20-fold excess of methanol. Obtained material was dried under vacuum at 40° C. to yield 5 as yellow amorphous powder (1.45 g, 57%).

(37) .sup.1H NMR (400 MHz, CDCl.sub.3 δ): 8.09 (d, J=1.7 Hz, 1H, 5-H, Ht), 7.81 (s, 1H, 4-H, Ht), 7.54-7.50 (m, 1H, 6-H, Ht), 7.33-7.27 (m, 3H, Ht), 7.26 (s, 1H, 7-H, Ht), 7.08 (d, J=8.8 Hz, 4H, p-Ph), 6.84 (d, J=8.8 Hz, 4H, p-Ph), 6.68 (d, J=8.8 Hz, 4H, p-Ph), 6.55 (d, J=8.8 Hz, 4H, p-Ph), 5.90 (s, 2H, NCH), 4.27 (t, J=7.0 Hz, 2H, NCH.sub.2), 3.85 (s, 6H, OCH.sub.3), 3.78 (s, 6H, OCH.sub.3), 1.43 (s, 9H, C(CH.sub.3)3), 1.47-1.39 (m, 2H, CH.sub.2), 0.96 (t, J=7.3 Hz, 3H, CH.sub.3).

(38) .sup.13C NMR (100 MHz, CDCl.sub.3 δ): 159.0, 158.7, 141.7, 139.5, 139.4, 138.9, 137.4, 134.9, 133.2, 130.8, 129.6, 129.5, 128.9, 128.1, 123.8, 122.3, 117.2, 116.6, 114.0, 113.2, 109.0, 108.7, 108.2, 55.6 (OCH.sub.3), 55.4 (OCH.sub.3), 43.1 (CH.sub.2), 34.9 (CH.sub.2), 32.2 (CH.sub.2), 31.5 (CH.sub.3), 23.8 (CH.sub.3), 20.8 (CH.sub.3), 14.1 (CH.sub.3).

(39) Elemental analysis: Calculated, %: C, 81.01; H, 7.06; N, 3.63. C.sub.52H.sub.54N.sub.2O.sub.4. Found, %: C, 80.81; H, 6.86; N, 3.43.

Example 6

4-{N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]amino}triphenylamine (see Scheme 2, Compound 6 or V-1012)

(40) ##STR00023##

(41) 4-aminotriphenylamine (1 g, 3.8 mmol) is dissolved in toluene (18 ml), (+/−)10-camphorsulfonic acid (1 g, 4.3 mmol) was added and reaction mixture was refluxed for 20 min. Then 2,2-bis(4-methoxyphenyl)acetaldehyde (2.46 g, 9.6 mmol) was added and reaction was continued using Dean-Stark apparatus for another 30 min. After reaction was finished (TLC, THF:n-hexane/v:v, 1:4) reaction mixture was extracted with ethyl acetate, organic layer dried with anhydrous Na.sub.2SO.sub.4, filtered and organic solvents removed in vacuum. The residue was purified by column chromatography using THF: n-hexane/v:v, 1:24 and precipitated from 20% solution in THF to 20-fold excess of methanol. Obtained material was dried under vacuum at 40° C. to yield 6 as yellow amorphous powder (1.6 g, 58%).

(42) .sup.1H NMR (400 MHz, CDCl.sub.3, 6): 7.31-7.22 (m, 4H, Ar), 7.15-6.93 (m, 14H, Ar), 6.88 (d, J=8.3 Hz, 4H, p-Ph), 6.67 (d, J=8.3 Hz, 4H, p-Ph), 6.53 (d, J=8.3 Hz, 4H, p-Ph), 5.83 (pl.s, 2H, NCH), 3.89 (s, 6H, OCH.sub.3), 3.78 (s, 6H, OCH.sub.3).

(43) .sup.13C NMR (100 MHz, CDCl.sub.3, δ): 158.9, 158.6, 148.1, 141.8, 134.4, 132.7, 136.7, 130.2, 129.1, 128.8, 126.4, 123.2, 122.0, 117.9, 114.4, 113.8, 113.0, 99.9, 55.4 (OCH.sub.3), 55.2 (OCH.sub.3).

(44) Elemental analysis: Calculated, %: C, 81.50; H, 6.02; N, 3.80. C.sub.50H.sub.44N.sub.2O.sub.4. Found, %: C, 81.20; H, 5.82; N, 3.48.

Example 7

9-butyl-3,6-bis{N.SUP.3.,N.SUP.3.,N.SUP.6.,N.SUP.6.-tetrakis(2,2-bis[4-methoxyphenyl)vinyl]amino}-9H-carbazole (see Scheme 3, Compound 7 or V-1020)

(45) ##STR00024##

(46) 9-butylcarbazole-3,6-diamine (1 g, 4.8 mmol) is dissolved in toluene (21 ml), (+/−)10-camphorsulfonic acid (1 g, 4.3 mmol) was added and reaction mixture was refluxed for 20 min. Then 2,2-bis(4-methoxyphenyl)acetaldehyde (5.04 g, 19.7 mmol) was added and reaction was continued using Dean-Stark apparatus for another 1 h. After reaction was finished (TLC, acetone:n-hexane/v:v, 1:4) reaction mixture was extracted with ethyl acetate, organic layer dried with anhydrous Na.sub.2SO.sub.4, filtered and organic solvents removed in vacuum. The residue was purified by column chromatography using acetone: n-hexane/v:v, 3:22 and precipitated from 20% solution in THF to 20-fold excess of methanol. Obtained material was dried under vacuum at 40° C. to yield 7 as yellow amorphous powder (3.2 g, 55%).

(47) .sup.1H NMR (400 MHz, CDCl.sub.3 δ): 7.76 (s, 2H, 4,5-H, Ht), 7.35-7.26 (m, 4H, 1,2,7,8-H, Ht), 7.06 (d, J=8.7 Hz, 8H, p-Ph), 6.82 (d, J=8.2 Hz, 8H, p-Ph), 6.63 (d, J=8.2 Hz, 8H, p-Ph), 6.49 (d, J=8.7 Hz, 8H, p-Ph), 5.86 (s, 4H, ═CH), 4.27 (s, 2H, NCH.sub.2), 3.84-3.81 (m, 12H, OCH.sub.3), 3.77-3.74 (m, 12H, OCH.sub.3), 1.87-1.83 (m, 2H, N CH.sub.2CH.sub.2), 1.44-1.39 (m, 2H, NCH.sub.2CH.sub.2CH.sub.2), 0.96 (t, J=7.3 Hz, 3H, CH.sub.3).

(48) .sup.13C NMR (100 MHz, CDCl.sub.3 δ): 158.9, 158.6, 147.9, 143.7, 134.9, 133.2, 130.8, 128.9, 126.7, 117.6, 113.9, 113.1, 111.5, 109.0, 89.6, 84.5, 55.6 (OCH.sub.3), 55.4 (OCH.sub.3), 23.0 (CH.sub.2), 20.7 (CH.sub.2), 16.7 (CH.sub.2), 14.1 (CH.sub.2).

(49) Elemental analysis: Calculated, %: C, 79.64; H, 6.27; N, 3.48. C.sub.80H.sub.75N.sub.3O.sub.8. Found, %: C, 79.44; H, 6.07; N, 3.28.

Example 8

9-(2-ethylhexyl)-3,6-bis{N.SUP.3.,N.SUP.3.,N.SUP.6.,N.SUP.6.-tetrakis(2,2-bis[4-methoxyphenyl)vinyl]amino}-9H-carbazole (see Scheme 3, Compound 8 or V-1021)

(50) ##STR00025##

(51) 9-(2-ethylhexyl)carbazole-3,6-diamine (1 g, 3.2 mmol) is dissolved in toluene (17 ml), (+/−)10-camphorsulfonic acid (1 g, 4.3 mmol) was added and reaction mixture was refluxed for min. Then 2,2-bis(4-methoxyphenyl)acetaldehyde (4.1 g, 16 mmol) was added and reaction was continued using Dean-Stark apparatus for another 1.5 h. After reaction was finished (TLC, acetone:n-hexane/v:v, 1:4) reaction mixture was extracted with ethyl acetate, organic layer dried with anhydrous Na.sub.2SO.sub.4, filtered and organic solvents removed in vacuum. The residue was purified by column chromatography using acetone: n-hexane/v:v, 3:22 and precipitated from 20% solution in THF to 20-fold excess of methanol. Obtained material was dried under vacuum at 40° C. to yield 8 as yellow amorphous powder (2 g, 49%).

(52) .sup.1H NMR (400 MHz, CDCl.sub.3 δ): 7.76 (s, 2H, 4,5-H, Ht), 7.35-7.26 (m, 4H, 1,2,7,8-H, Ht), 7.06 (d, J=8.6 Hz, 8H, p-Ph), 6.82 (d, J=8.3 Hz, 8H, p-Ph), 6.67-6.60 (m, 8H, p-Ph), 6.49 (d, J=8.6 Hz, 8H, p-Ph), 5.86 (s, 4H, ═CH), 4.11 (d, J=8.3 Hz, 2H, NCH.sub.2), 3.84 (s, 12H, OCH.sub.3), 3.74 (s, 12H, OCH.sub.3), 2.04 (s, 1H, NCH.sub.2CH), 1.45-1.26 (m, 8H, NCH.sub.2CH(CH.sub.2)4), 0.91 (m, 6H, (CH.sub.3)2).

(53) .sup.13C NMR (100 MHz, CDCl.sub.3 δ): 158.9, 158.6, 144.2, 143.6, 140.6, 134.9, 133.2, 130.9, 129.6, 128.9, 128.0, 123.2, 119.7, 117.7, 117.6, 115.1, 114.6, 113.9, 113.1, 109.3, 89.5, 55.6 (OCH.sub.3), 55.4 (OCH.sub.3), 47.7 (CH), 39.6 (CH.sub.2), 32.8 (CH.sub.2), 31.1 (CH.sub.2), 29.0 (CH.sub.2), 23.3 (CH.sub.2), 14.3 (CH.sub.3), 11.0 (CH.sub.3).

(54) Elemental analysis: Calculated, %: C, 79.91; H, 6.63; N, 3.33. C.sub.84H.sub.83N.sub.3O.sub.8. Found, %: C, 79.71; H, 6.43; N, 3.13.

Example 9

N.SUP.3.,N.SUP.3.,N.SUP.6.,N.SUP.6.,9-pentakis(2,2-bis(4-methoxyphenyl)vinyl)-9H-carbazole-3,6-diamine (see Scheme 3, Compound 9 or V-1103)

(55) ##STR00026##

(56) A mixture of 9H-carbazole-3,6-diamine (0.5 g, 2.5 mmol), 2,2-bis(4-methoxyphenyl)acetaldehyde (4.06 g, 15.8 mmol) and camphor-10-sulfonic acid (0.59 g, 2.5 mmol) were dissolved in THF (10 ml+volume of the Dean-Stark trap ml), 3 Å molecular sieves were added to absorb water. The mixture was heated under argon for 8 hours at reflux. Afterwards (TLC control 7:18 v/v acetone/n-hexane) the reaction mixture was cooled to room temperature and poured into 200 ml of ethanol. The precipitate was filtered and washed with 200 ml of ethanol and then crystalized from acetone giving compound 9 as yellow crystals (m. p. 187-189° C.). Yield: 2.05 g (58%).

(57) Elemental analysis calcd (%) for C92H81N3O10 (1387.59 g/mol): C, 79.57; H, 5.88; N, 3.03. Found: C, 79.31; H, 6.01; N, 3.16.

(58) 1H NMR (700 MHz, CDCl.sub.3) δ 7.69 (s, 2H), 7.38 (d, 8.7 Hz, 2H), 7.18-7.10 (m, 4H), 7.04 (dd, J=28.6, 8.5 Hz, 10H), 6.97-6.88 (m, 2H), 6.86-6.75 (m, 8H), 6.70-6.55 (m, 11H), 6.53-6.42 (m, 8H), 5.81 (s, 4H), 3.89-3.69 (m, 30H).

(59) 13C NMR (176 MHz, CDCl3) δ 159.78, 158.87, 158.85, 158.50, 136.58, 134.61, 133.63, 133.00, 131.14, 130.80, 130.66, 130.15, 129.94, 129.68, 128.81, 127.68, 124.24, 117.27, 114.39, 113.80, 113.74, 112.97, 110.98, 108.74, 55.40, 55.40, 55.19.

(60) Elemental analysis calcd (%) for C92H81N3O10 (1387.59 g/mol): C, 79.57; H, 5.88; N, 3.03. Found: C, 79.31; H, 6.01; N, 3.16.

Example 10

N.SUP.2.,N.SUP.2.,N.SUP.7.,N.SUP.7.-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9H-fluorene-2,7-diamine (see Scheme 4, Compound 10 or V-1275)

(61) ##STR00027##

(62) 2,7-diaminofluorene (0.3 g, 1.5 mmol) was dissolved in tetrahydrofuran (9 ml+volume of the Dean-Stark trap), (+/−)camphor-10-sulphonic acid (0.36 g, 1.5 mmol) was added and the mixture was heated at reflux for 20 minutes. Afterwards, 2,2-bis(4-methoxyphenyl)acetaldehyde (2.4 g, 9.2 mmol) was added and reflux was continued using a Dean-Stark trap for 6 hours. After cooling to room temperature, reaction mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and solvent evaporated. The crude product was crystallized from ethanol (30 ml). The obtained crystals were filtered off and washed with hot ethanol for three times. The product was recrystallized from acetone/ethanol 1:1 gave as light yellow-green crystals (1.14 g, 60%). .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.60 (d, J=8.4 Hz, 2H), 7.34-7.20 (m, 2H), 7.19-6.94 (m, 10H), 6.84 (d, J=8.4 Hz, 8H), 6.67 (d, J=8.4 Hz, 8H), 6.49 (d, J=8.4 Hz, 8H), 5.82 (s, 4H), 4.04-3.57 (m, 26H).

(63) .sup.13C NMR (101 Mhz, CDCl.sub.3) δ 159.01, 158.71, 144.37, 132.82, 130.66, 130.18, 128.85, 114.43, 113.92, 113.63, 113.05, 55.46, 55.26, 37.05 ppm.

(64) Anal. calcd for C.sub.77H.sub.68N.sub.2O.sub.8: C, 80.46; H, 5.96; N, 2.44. found: C, 80.14; H, 5.82; N, 2.48.

Example 11

N.SUP.2.,N.SUP.2.,N.SUP.7.,N.SUP.7.-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9-dimethyl-9H-fluorene-2,7-diamine (see Scheme 4, Compound 11 or V-1237)

(65) ##STR00028##

(66) Compound 10 (0.5 g, 0.4 mmol) in dimethylsulfoxyde (20 ml) was dissolved and purged with argon for 30 minutes. Afterwards, benzyltriethylammonium chloride (0.01 g, 0.04 mmol) and 50% NaOH (0.15 ml) solution were added. The color of the reaction turned black and then iodomethane (0.14 g, 1.0 mmol) was slowly added dropwise under argon atmosphere and stirred at room temperature for 120 hours. The reaction mixture was filtered off and washed with water three times. The crude product was purified by column chromatography using 1:4 v/v tetrahydrofuran/n-hexane as an eluent to collect product 11 as a yellow solid (0.26 g, 51%).

(67) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.54 (d, J=8.0 Hz, 2H), 7.19-6.94 (m, 12H), 6.87 (d, J=8.4 Hz, 8H), 6.66 (d, J=8.4 Hz, 8H), 6.53 (d, J=8.4 Hz, 8H), 5.96-5.70 (m, 4H), 3.84 (d, J=36.8, 24H), 1.46 (s, 6H).

(68) .sup.13C NMR (101 MHz, CDCl.sub.3) δ 158.98, 158.68, 155.02, 132.82, 132.23, 130.65, 128.90, 116.10, 113.90, 113.01, 111.03, 55.43, 55.24, 47.14, 27.56 ppm.

(69) Anal. calcd for C.sub.79H.sub.72N.sub.2O.sub.8: C, 80.59; H, 6.16; N, 2.38. found: C, 80.74; H, 6.11; N, 2.35.

Example 12

N.SUP.2.,N.SUP.2.,N.SUP.7.,N.SUP.7.-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9-dipropyl-9H-fluorene-2,7-diamine (see Scheme 4, Compound 12 or V-1235)

(70) ##STR00029##

(71) Compound 10 (0.5 g, 0.4 mmol) in dimethylsulfoxyde (20 ml) was dissolved and purged with argon for 30 minutes. Afterwards, benzyltriethylammonium chloride (0.01 g, 0.04 mmol) and 50% NaOH (0.15 ml) solution were added. The color of the reaction turned black and then bromopropane (0.12 g, 1.0 mmol) was slowly added dropwise under argon atmosphere and stirred at room temperature for 72 hours. The reaction mixture was filtered off and washed with water three times. The crude product was purified by column chromatography using 1:4 v/v tetrahydrofuran/n-hexane as an eluent to collect product 12 as a yellow solid (0.28 g, 52%).

(72) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.48 (d, J=8.0 Hz, 2H), 7.12-6.94 (m, 12H), 6.85 (d, J=8.8 Hz, 8H), 6.66 (d, J=8.8 Hz, 8H), 6.51 (d, J=8.8 Hz, 8H), 5.81 (s, 4H), 3.81 (d, J=37.2 Hz, 24H), 1.99-1.81 (m, 4H), 0.88-0.60 (m, 10H).

(73) .sup.13C NMR (101 MHz, CDCl.sub.3) δ 158.79, 158.54, 149.08, 134.23, 132.65, 130.45, 128.79, 119.03, 113.71, 112.84, 111.90, 59.52, 55.25, 55.07, 17.74, 14.12, 11.52 ppm.

(74) Anal. calcd for C.sub.83H.sub.80N.sub.2O.sub.8: C, 80.82; H, 6.54; N, 2.27. found: C, 80.64; H, 6.61; N, 2.30.

Example 13

N.SUP.2.,N.SUP.2.,N.SUP.7.,N.SUP.7.-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9-dihexyl-9H-fluorene-2,7-diamine (see Scheme 4, Compound 13 or V-1236)

(75) ##STR00030##

(76) Compound 10 (0.5 g, 0.4 mmol) in dimethylsulfoxyde (20 ml) was dissolved and purged with argon for 30 minutes. Afterwards, benzyltriethylammonium chloride (0.01 g, 0.04 mmol) and 50% NaOH (0.15 ml) solution were added. The color of the reaction turned black and then bromohexane (0.16 g, 1.0 mmol) was slowly added dropwise under argon atmosphere and stirred at room temperature for 26 hours. The reaction mixture was filtered off and washed repeatedly with water three times. The crude product was purified by column chromatography using 4:21 v/v tetrahydrofuran/n-hexane as an eluent to collect product 13 a yellow solid (0.36 g, 63%).

(77) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.52 (d, J=8.0 Hz, 2H), 7.12-6.93 (m, 12H), 6.85 (d, J=8.4 Hz, 8H), 6.65 (d, J=8.4 Hz, 8H), 6.50 (d, J=8.8 Hz, 8H), 5.81 (s, 4H), 3.81 (d, J=38.0 Hz, 24H), 1.97-1.82 (m, 4H), 1.21-1.01 (m, 12H), 0.85-0.66 (m, 10H) ppm.

(78) .sup.13C NMR (101 MHz, CDCl.sub.3) δ 158.99, 158.69, 152.04, 134.48, 132.95, 130.64, 128.90, 119.25, 115.91, 113.92, 113.02, 111.31, 55.38, 55.26, 40.11, 31.39, 29.38, 23.62, 22.48, 14.12 ppm.

(79) Anal. calcd for C.sub.89H.sub.92N.sub.2O.sub.8: C, 81.12; H, 7.04; N, 2.13. found: C, 81.24; H, 7.11; N, 2.10.

Example 14

9,9-dibenzyl-N.SUP.2.,N.SUP.2.,N.SUP.7.,N.SUP.7.-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9H-fluorene-2,7-diamine (see Scheme 4, Compound 14 or V-1227)

(80) ##STR00031##

(81) Compound 10 (0.5 g, 0.4 mmol) in dimethylsulfoxyde (20 ml) was dissolved and purged with argon for 30 minutes. Afterwards, benzyltriethylammonium chloride (0.01 g, 0.04 mmol) and 50% NaOH (0.15 ml) solution were added. The color of the reaction turned black and then benzyl bromide (0.16 g, 1.0 mmol) was slowly added dropwise under argon atmosphere and stirred at room temperature for 96 hours. The reaction mixture was filtered off and washed with water three times. The crude product was purified by column chromatography using 1:4 v/v tetrahydrofuran/n-hexane as an eluent to collect product 14 as a pale brown solid (0.29 g, 50%).

(82) .sup.1H NMR (400 MHz, acetone-d.sub.6) δ 7.56 (d, J=8.0 Hz, 2H), 7.31-6.78 (m, 30H), 6.71 (d, J=8.4 Hz, 8H), 6.50 (d, J=8.4 Hz, 8H), 5.97-5.66 (m, 4H), 3.85 (d, J=48.8 Hz, 24H), 3.53-3.14 (m, 4H).

(83) .sup.13C NMR (101 MHz, acetone) δ 159.35, 159.03, 148.60, 136.29, 134.30, 132.53, 130.68, 130.54, 128.84, 127.22, 127.14, 126.52, 113.86, 113.50, 112.98, 60.05, 54.88, 54.61, 10.95 ppm.

(84) Anal. calcd for C.sub.91H.sub.80N.sub.2O.sub.8: C, 82.20; H, 6.06; N, 2.11. found: C, 82.54; H, 6.11; N, 2.15.

Example 15

N,N-bis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluoren]-2-amine (see Scheme 5, Compound 15 or V-1305)

(85) ##STR00032##

(86) 9,9′-spirobi[9H-fluoren]-2-amine (0.30 g, 0.91 mmol) was dissolved in tetrahydrofuran (9 ml+volume of the Dean-Stark trap), (+/−)camphor-10-sulphonic acid (0.21 g, 0.91 mmol) was added and the mixture was heated at reflux for 20 minutes. Afterwards, 2,2-bis(4-methoxyphenyl)acetaldehyde (0.70 g, 2.72 mmol) was added, and reflux continued using a Dean-Stark trap. After termination of the reaction (6 h, TLC, THF:n-hexane, 7:18) the reaction mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and solvent evaporated. The crude product was purified by column chromatography using THF:n-hexane (v:v; 4:21) eluent. The obtained product was precipitated from THF into 20-fold excess of methanol. The precipitate was filtered off and washed with methanol to collect product 15 as a yellow solid (0.36 g, 49%).

(87) .sup.1H NMR (400 MHz, THF-d.sub.8) δ: 7.83 (d, J=8.3 Hz, 1H); 7.79 (d, J=7.6 Hz, 3H); 7.33-7.21 (m, 3H); 7.16 (dd, J=8.3, 2.2 Hz, 1H); 7.09 (t, J=6.9 Hz, 2H); 6.94 (t, J=6.9 Hz, 1H); 6.85 (d, J=8.7 Hz, 4H); 6.77 (d, J=8.8 Hz, 4H); 6.72 (d, J=7.6 Hz, 2H); 6.53 (d, J=8.8 Hz, 4H); 6.50-6.44 (m, 2H); 6.33 (d, J=8.7 Hz, 4H); 5.60 (s, 2H); 3.78 (s, 6H); 3.66 (s, 6H) ppm.

(88) .sup.13C NMR (101 MHz, THF) δ: 160.44; 160.13; 151.16; 150.20; 150.12; 147.58; 142.88; 142.62; 137.27; 135.19; 133.62; 132.08; 131.50; 129.83; 128.66; 128.62; 128.49; 127.57; 127.49; 124.89; 124.41; 121.55; 121.01; 120.09; 118.07; 114.75; 113.76; 112.91; 66.50; 55.69; 55.44 ppm.

(89) Anal. calcd for C.sub.57H.sub.45NO.sub.4: C, 84.73; H, 5.61; N, 1.73. found: C, 84.59; H, 5.69; N, 1.92.

Example 16

N.SUP.2.,N.SUP.2.,N.SUP.2.′,N.SUP.2.′-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluorene]-2,2′-diamine (see Scheme 5, Compound 16 or V-1306)

(90) ##STR00033##

(91) 9,9′-spirobi[fluorene]-2,2′-diamine (0.20 g, 0.58 mmol) was dissolved in toluene (7 ml+volume of the Dean-Stark trap), (+/−)camphor-10-sulphonic acid (0.13 g, 0.58 mmol) was added and the mixture was heated at reflux for 20 minutes. Afterwards, 2,2-bis(4-methoxyphenyl)acetaldehyde (0.89 g, 3.46 mmol) was added, and reflux continued using a Dean-Stark trap. After termination of the reaction (6 h, TLC, THF:n-hexane, 2:3) the reaction mixture was extracted with dichloromethane. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and solvent evaporated. The crude product was purified by column chromatography using THF:n-hexane (v:v; 7:18) eluent. The obtained product was precipitated from THF into 20-fold excess of methanol. The precipitate was filtered off and washed with methanol to collect product 16 as a yellow solid (0.23 g, 31%).

(92) .sup.1H NMR (400 MHz, THF-d.sub.8) δ: 7.74 (d, J=8.3 Hz, 2H); 7.70 (d, J=7.6 Hz, 2H); 7.21 (t, J=7.0 Hz, 2H); 7.10 (dd, J=8.3, 2.2 Hz, 2H); 6.96 (t, J=7.5 Hz, 2H); 6.89 (d, J=8.8 Hz, 8H); 6.79 (d, J=8.8 Hz, 8H); 6.62-6.52 (m, 12H); 6.36 (d, J=8.8 Hz, 8H); 5.63 (s, 4H); 3.80 (s, 12H); 3.69 (s, 12H) ppm.

(93) .sup.13C NMR (101 MHz; THF) δ: 160.48; 160.17; 151.32; 150.51; 147.54; 142.40; 137.19; 135.13; 133.73; 132.28; 131.50; 129.88; 128.44; 127.69; 127.46; 124.33; 121.64; 120.08; 117.85; 114.90; 113.81; 112.52; 66.50; 55.72; 55.46 ppm.

(94) Anal. calcd for C.sub.89H.sub.74N.sub.2O.sub.8: C, 82.26; H, 5.74; N, 2.16. found: C, 79.33; H, 6.66; N, 2.08.

Example 17

N.SUP.2.,N.SUP.2.,N.SUP.7.,N.SUP.7.-tetrakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluorene]-2,7-diamine (see Scheme 5, Compound 17 or V-1308)

(95) ##STR00034##

(96) 9,9′-spirobi[fluorene]-2,7-diamine (0.14 g, 0.42 mmol) was dissolved in toluene (5 ml+volume of the Dean-Stark trap), (+/−)camphor-10-sulphonic acid (0.10 g, 0.42 mmol) was added and the mixture was heated at reflux for 20 minutes. Afterwards, 2,2-bis(4-methoxyphenyl)acetaldehyde (0.64 g, 2.50 mmol) was added, and reflux continued using a Dean-Stark trap. After termination of the reaction (5 h, TLC, acetone:n-hexane, 7:18) the reaction mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and solvent evaporated. The crude product was purified by column chromatography using THF:n-hexane (v:v; 7:18) eluent. The obtained product was precipitated from THF into 20-fold excess of methanol. The precipitate was filtered off and washed with methanol to collect product 17 as a yellow solid (0.22 g, 42%).

(97) .sup.1H NMR (400 MHz, THF-d.sub.8) δ: 7.75 (d, J=8.3 Hz, 2H); 7.68 (d, J=7.5 Hz, 2H); 7.23 (t, J=7.0 Hz, 2H); 7.11 (dd, J=8.2, 2.5 Hz, 4H); 6.87-6.72 (m, 18H); 6.52 (d, J=8.8 Hz, 8H); 6.32 (d, J=8.8 Hz, 10H); 5.56 (s, 4H); 3.78 (s, 12H); 3.66 (s, 12H) ppm.

(98) .sup.13C NMR (101 MHz, THF) δ: 160.39; 160.08; 151.35; 150.36; 146.67; 142.81; 137.14; 135.27; 133.68; 131.71; 131.52; 129.80; 128.62; 128.60; 127.65; 124.92; 121.12; 120.65; 118.22; 114.72; 113.74; 112.85; 66.50; 55.68; 55.42 ppm.

(99) Anal. calcd for C.sub.89H.sub.74N.sub.2O.sub.8: C, 82.26; H, 5.74; N, 2.16. found: C, 82.14; H, 5.43; N, 2.5.

Example 18

N.SUP.2.,N.SUP.2.,N.SUP.2.′,N.SUP.2.′,N.SUP.7.,N.SUP.7.,N.SUP.7.′,N.SUP.7.′-octakis[2,2-bis(4-methoxyphenyl)vinyl]-9,9′-spirobi[fluorene]-2,2′,7,7′-tetraamine (see Scheme 5, Compound 18 or V-1307)

(100) ##STR00035##

(101) 2,2′,7,7′-Tetraamino-9,9′-spirobifluorene (0.20 g, 0.53 mmol) was dissolved in toluene (7 ml+volume of the Dean-Stark trap), (+/−)camphor-10-sulphonic acid (0.12 g, 0.53 mmol) was added and the mixture was heated at reflux for 20 minutes. Afterwards, 2,2-bis(4-methoxyphenyl)acetaldehyde (1.63 g, 6.36 mmol) was added, and reflux continued using a Dean-Stark trap. After termination of the reaction (5 h, TLC, acetone:n-hexane, 2:3) the reaction mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and solvent evaporated. The crude product was purified by column chromatography using acetone:n-hexane (v:v; 8:17) eluent. The obtained product was precipitated from THF into 20-fold excess of methanol. The precipitate was filtered off and washed with methanol to collect product 18 as a yellow solid (0.4 g, 33%).

(102) .sup.1H NMR (400 MHz, THF-d.sub.8) δ: 7.55 (d, J=8.3 Hz, 4H); 6.98 (dd, J=8.3, 2.2 Hz, 4H); 6.91 (d, J=8.7 Hz, 16H); 6.83 (d, J=8.8 Hz, 16H); 6.61 (d, J=8.8 Hz, 16H); 6.50 (d, J=2.2 Hz, 4H); 6.40 (d, J=8.8 Hz, 16H); 5.65 (s, 8H); 3.86 (s, 24H); 3.70 (s, 24H) ppm.

(103) .sup.13C NMR (101 MHz, THF) δ: 160.49; 160.13; 151.90; 146.56; 136.85; 135.24; 133.90; 132.05; 131.53; 129.94; 127.92; 120.79; 117.79; 114.97; 113.82; 112.19; 66.50; 55.78; 55.45 ppm.

(104) Anal. calcd for C.sub.153H.sub.132N.sub.4O.sub.16: C, 80.50; H, 5.83; N, 2.45. found: C, 77.9; H, 5.7; N, 2.46.

Example 19

(105) Ionization Potential Measurements

(106) The solid state ionization potential (I.sub.p) of the layers of the compounds of formulae (1) to (18) was measured by the electron photoemission in air method (E. Miyamoto, Y. Yamaguchi, M. Masaaki, Electrophotography, 1989, vol. 28, pp. 364). The samples for the ionization potential measurement were prepared by dissolving materials in THF and were coated on Al plates pre-coated with ˜0.5 μm thick methylmethacrylate and methacrylic acid copolymer adhesive layer. The thickness of the transporting material layer was 0.5.sup.−1 μm. Photoemission experiments are carried out in vacuum and high vacuum is one of the main requirements for these measurements. If vacuum is not high enough the sample surface oxidation and gas adsorption are influencing the measurement results. In our case, however, the organic materials investigated are stable enough to oxygen and the measurements may be carried out in the air. The samples were illuminated with monochromatic light from the quartz monochromator with deuterium lamp. The power of the incident light beam was (2-5).Math.10.sup.−8 W. The negative voltage of −300 V was supplied to the sample substrate. The counter-electrode with the 4.5×15 mm.sup.2 slit for illumination was placed at 8 mm distance from the sample surface. The counter-electrode was connected to the input of the BK2-16 type electrometer, working in the open input regime, for the photocurrent measurement. The 10.sup.−15-10.sup.−12 A strong photocurrent was flowing in the circuit under illumination. The photocurrent I is strongly dependent on the incident light photon energy hν. The I.sup.0.5=f(hν) dependence was plotted. Usually the dependence of the photocurrent on incident light quanta energy is well described by linear relationship between I.sup.0.5 and hν near the threshold. The linear part of this dependence was extrapolated to the hν axis and I.sub.p value was determined as the photon energy at the interception point. The I.sub.p results are presented in Table 1.

Example 20

(107) Hole Drift Mobility Measurements

(108) The samples for the hole mobility measurements were prepared by spin-coating the solutions of the synthesized compounds 1-18 on the polyester films with conductive Al layer. THF was used for 1-6, 9-18 compounds, as chlorobenzene for 7 and 8 compounds as well. The layer thickness was in the range of 5-10 μm. The hole drift mobility was measured by xerographic time of flight technique (XTOF) (Vaezi-Nejad, S. M., Int. J. Electronics, 1987, 62, No 3, 361-384). Electric field was created by positive corona charging. The charge carriers were generated at the layer surface by illumination with pulses of nitrogen laser (pulse duration was 2 ns, wavelength 337 nm). The layer surface potential decrease as a result of pulse illumination was up to 1-5% of initial potential before illumination. The capacitance probe that was connected to the wide frequency band electrometer measured the speed of the surface potential decrease dU/dt. The transit time t.sub.t was determined by the kink on the curve of the dU/dt transient in double logarithmic scale. The drift mobility was calculated by the formula μ=d.sup.2/U.sub.0t.sub.t, where d is the layer thickness, U.sub.0—the surface potential at the moment of illumination. The p results are presented in Table 1.

(109) TABLE-US-00001 TABLE 1 Ionization potential (I.sub.p) and charge mobility values (μ) of the hole transporting compounds 1-18 and Spiro-OMeTAD Mobility Mobility μ.sub.0, cm.sup.2V.sup.−1s.sup.−1 cm.sup.2V.sup.−1s.sup.−1 (at 6.4 .Math. 10.sup.5 No. Formula Ip, eV (at 0 V/cm) V/cm)  1 or V-950 5.01 1.98 .Math. 10.sup.−5   8 .Math. 10.sup.−4  2 or V-1013 4.97 1.13 .Math. 10.sup.−5 5.5 .Math. 10.sup.−4  3 or V-1001 5.01  2.7 .Math. 10.sup.−5 9.4 .Math. 10.sup.−4  4 or V-1000 5.00  3.2 .Math. 10.sup.−5   9 .Math. 10.sup.−4  5 or V-1004 0 5.00  1.2 .Math. 10.sup.−5 4.6 .Math. 10.sup.−4  6 or V-1012 5.11  2.6 .Math. 10.sup.−5 5.0 .Math. 10.sup.−4  7 or V-1020 5.00  1.2 .Math. 10.sup.−4 1.1 .Math. 10.sup.−3  8 or V-2021 4.93   6 .Math. 10.sup.−5 2.1 .Math. 10.sup.−3  9 or V-1103 5.01  3.7 .Math. 10.sup.−5 7.8 .Math. 10.sup.−4 10 or V-1275 5.01  1.2 .Math. 10.sup.−4 5.3 .Math. 10.sup.−3 11 or V-1237 5.0  1.2 .Math. 10.sup.−4 3.8 .Math. 10.sup.−3 12 or V-1235 5.03  3.3 .Math. 10.sup.−4 2.8 .Math. 10.sup.−3 13 or V-1236 5.03  2.6 .Math. 10.sup.−4 3.6 .Math. 10.sup.−3 14 or V-1227 4.9  8.0 .Math. 10.sup.−5 1.6 .Math. 10.sup.−3 15 or V-1305 0 5.2  1.7 .Math. 10.sup.−5 2.6 .Math. 10.sup.−4 16 or V-1306 5.2  5.4 .Math. 10.sup.−6 2.3 .Math. 10.sup.−4 17 or V-1308 5.0  9.4 .Math. 10.sup.−4 2.1 .Math. 10.sup.−3 18 or V-1307 5.0  6.4 .Math. 10.sup.−4 1.4 .Math. 10.sup.−3 Spiro- OMeTAD 5.00  4.1 .Math. 10.sup.−5   5 .Math. 10.sup.−4

(110) The estimated I.sub.p values of all synthesized compounds are in range 4.90 eV-5.20 eV and are very closed to the value of Spiro-OMeTAD (5.0 eV). The measured charge mobility values of synthesized compounds 1-6, 8, 9, and 14-16 are also comparable to the values measured for Spiro-OMeTAD, while charge mobility of the compounds 7, 10-13, 17, and 18 increase by c.a. one order of magnitude (μ.sub.0=10.sup.−4 cm.sup.2 V.sup.−1 S.sup.−1) at weak electric fields.

Example 21

(111) Photovoltaic Characterization of Compound of Formula (I) Corresponding to Compound V-950

(112) The performance of hole transporter V-950 is tested in mixed perovskite-based solar cells using a mesoporous TiO.sub.2 photo-anode and an Au cathode (FTO/compact TiO.sub.2/mesoporous compact TiO.sub.2/mixed perovskite/V-950/Au), following a procedure described in the literature (T. J. Jacobsson, J. P. Correa-Baena, M. Pazoki, M. Saliba, K. Schenk, M. Gratzel and A. Hagfeldt. Energy Environ. Sci., 2016, 9, 1706-1724). The mixtures of cations (methyl ammonia (MA), formamidinium (FA)) and anions (I, Br) were used for preparation of the mixed perovskite. The obtained device shows a maximum PCE of 17.8% under AM 1.5 G illumination. The measured fill factor is 0.74, the current density (J.sub.SC) 22.5 mA/cm.sup.2 and the open-circuit voltage (V.sub.OC) is found to be 1.07 V (FIG. 1). The high J.sub.SC indicates that the photogenerated charge carriers are efficiently extracted and the high V.sub.OC reveals possibly good energy level alignment between perovskite valence band and the HOMO of V-950. This high V.sub.OC also indicates slow recombination between injected holes and electrons from either the perovskite capping layer or TiO.sub.2. Current Density-Voltage (J-V) characteristics of compound (1) corresponding to compound V-950 and Spiro-OMeTAD are presented in FIG. 1. The incident photon-to-current efficiency (IPCE) (FIG. 2) of the device as a function of wavelength indicates that the device with V950 as the HTM exhibits IPCE above 90% from 400 nm covering the entire visible region to 700 nm.

(113) The device characteristics demonstrate that performance of the investigated HTM is on par with Spiro-OMeTAD.