Synthons for developing organic semiconductors

Abstract

A process for the synthesis of -conjugated materials including a step of utilizing a synthon having a carbazole or fluorene nucleus.

Claims

1. A process for the synthesis of -conjugated materials of formula (1b) ##STR00049## in which ##STR00050## represents a central polyfunctional unit bearing functions allowing grafting in position 9 of the carbazole nucleus, n is an integer equal to or greater than 2, advantageously comprised between 2 and 5, R.sub.1 and R.sub.2, identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are selected independently of one another from the group comprising: i. hydrogen; ii. aryl groups, said aryl groups being able to be substituted by at least one straight or branched C.sub.1-C.sub.5 alkyl group; iii. ##STR00051## groups in which Ar.sub.1 and Ar.sub.2, identical or different, each represent independently of one another an aryl group, optionally substituted by one or more substituents, identical or different, selected from: a. a hydrogen atom; b. straight or branched C.sub.1-C.sub.12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; c. straight or branched C.sub.1-C.sub.12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; d. oligoethers; and e. oligothioethers, provided that R.sub.1 and R.sub.2 are not simultaneously a hydrogen atom, R.sub.3 and R.sub.4, identical or different, occupy the positions left free by R.sub.1 and R.sub.2 and are selected from: a. hydrogen; b. halogens; c. nitro group; d. sulphonate group; e. amine groups; f. carbonyl groups; g. mono- or polycyclic aromatic groups; h. straight or branched C.sub.1-C.sub.12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; i. straight or branched C.sub.1-C.sub.12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; j. oligoethers; and k. oligothioethers, the process comprising a step of reacting a synthon of formula (I) ##STR00052## in which W represents an N(H) group, R.sub.1 and R.sub.2, identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are selected independently of one another from the group comprising: i. hydrogen; ii. the mono- or polycyclic aromatic groups, said groups being able to be substituted by at least one straight or branched C.sub.1-C.sub.12 alkyl group, in particular a methyl group, or by a straight or branched C.sub.1-C.sub.12 alkoxy group, in particular a methoxy; iii. ##STR00053## groups in which Ar.sub.1 and Ar.sub.2, identical or different, each represent independently of one another an aryl group, optionally substituted by one or more substituents, identical or different, selected from: a. hydrogen atom; b. straight or branched C.sub.1-C.sub.12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; c. straight or branched C.sub.1-C.sub.12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S, d. oligoethers; and e. oligothioethers, provided that R.sub.1 and R.sub.2 are not simultaneously a hydrogen atom, R.sub.3 and R.sub.4, identical or different, occupy the positions left free by R.sub.1 and R.sub.2 and are selected from: a. hydrogen; b. halogens; c. a nitro group; d. a sulphonate group; e. amine groups; f. carbonyl groups; g. mono- or polycyclic aromatic groups; h. straight or branched C.sub.1-C.sub.12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; i. straight or branched C.sub.1-C.sub.12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; and j. oligoethers; with a compound of formula X-Q-X, in which X represents a halogen atom and Q represents a spacer selected from a group consisting of: C.sub.1-C.sub.12 alkylenyl groups, arylenyl groups, oligoethers and oligothioethers.

2. The process according to claim 1, characterized in that in the compound of formula (I), R.sub.1 and R.sub.2 each represent, independently of one another, a group selected from: i. the phenyl, naphthyl, anthracenyl, indenyl, biphenyl, terphenyl, carbazolyl groups, said groups being able to be substituted by at least one straight or branched C.sub.1-C.sub.12 alkyl group, in particular a methyl group; ii. ##STR00054## groups in which Ra and Rb, identical or different, each represent, independently of one another: a. either a hydrogen atom; b. or a straight or branched C.sub.1-C.sub.12 alkyl group, said alkyl group being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; c. or a straight or branched C.sub.1-C.sub.12 alkoxy group, said alkoxy group being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; d. or an oligoether; e. or an oligothioether.

3. The process according to claim 1, characterized in that in the compound of formula (I), R.sub.3 and R.sub.4 each represent a hydrogen atom.

4. The process for the synthesis of -conjugated materials according to claim 1, further comprising: a) a step of protecting W when W represents an N(H) group in the compound of formula (II) ##STR00055## and R.sub.3 and R.sub.4, identical or different, are selected from: i. hydrogen; ii. halogens; iii. a nitro group; iv. a sulphonate group; v. amine groups; vi. carbonyl groups; vii. mono- or polycyclic aromatic groups; viii. straight or branched C.sub.1-C.sub.12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; ix. straight or branched C.sub.1-C.sub.12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; x. oligoethers; and xi. oligothioethers, provided that if R.sub.3 is in position 2 then R.sub.4 is not in position 7 and if R.sub.3 is in position 3 then R.sub.4 is not in position 6, to give a compound of formula (III) ##STR00056## in which GP is an amine protecting group, b) treating the compound of formula (III) with a halogenated derivative, to give a compound of formula (IVb) ##STR00057## in which R.sub.3 and R.sub.4 are as defined in claim 1 and X, in position 3 and 6 of the carbazole represents a halogen atom, in particular an iodine or bromine atom, c) a coupling reaction of said compound of formula (IVb) to give a compound of formula (Vb) ##STR00058## in which R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as defined in claim 1.

5. A process for the synthesis of -conjugated materials of formula (Ib) ##STR00059## in which R.sub.1 and R.sub.2, identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are selected independently of one another from the group comprising: i. hydrogen; ii. the aryl groups, said aryl groups being able to be substituted by at least one straight or branched C.sub.1-C.sub.12 alkyl group, in particular a methyl group; iii. ##STR00060## groups in which A.sub.1 and A.sub.2, identical or different, each represent independently of one another an aryl group, optionally substituted by one or more substituents, identical or different, selected from: a. hydrogen atom; b. straight or branched C.sub.1-C.sub.12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; c. straight or branched C.sub.1-C.sub.12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; d. oligoethers; and e. oligothioethers, provided that R.sub.1 and R.sub.2 are not simultaneously a hydrogen atom, R.sub.3 and R.sub.4, identical or different, occupy the positions left free by R.sub.1 and R.sub.2 and are selected from: a. hydrogen; b. halogens; c. a nitro group; d. a sulphonate group; e. an amine group; f. a carbonyl group; g. mono- or polycyclic aromatic groups; h. straight or branched C.sub.1-C.sub.12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; i. straight or branched C.sub.1-C.sub.12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; f. oligoethers; and g. oligothioethers; and R.sub.6 represents either a straight or branched C.sub.1-C.sub.12 alkyl group, or a C.sub.6-C.sub.18 aryl group, in particular a benzene or methoxybenzene (anisole) group, or an amine protecting group, in particular a benzyl group, optionally substituted by a C.sub.1-C.sub.5 alkoxy group, or a C.sub.6-C.sub.18 aryl group substituted by a halogen, in particular fluorine or substituted by a straight or branched fluorinated C.sub.1-C.sub.12 alkyl group, in particular trifluoromethyl (CF.sub.3), or a bi-, tri or tetracyclic group comprising from 10 to 18 carbon atoms, such as for example a naphthyl, tetrahydronaphthyl, anthracenyl or pyrenyl group, the process comprising a step of reacting a synthon of formula (I) ##STR00061## in which W represents an N(H) group, R.sub.1 and R.sub.2, identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are selected independently of one another from the group comprising: i. hydrogen; ii. the mono- or polycyclic aromatic groups, said groups being able to be substituted by at least one straight or branched C.sub.1-C.sub.12 alkyl group, in particular a methyl group, or by a straight or branched C.sub.1-C.sub.12 alkoxy group, in particular a methoxy; iii. ##STR00062## groups in which A.sub.1and A.sub.2, identical or different, each represent independently of one another an aryl group, optionally substituted by one or more substituents, identical or different, selected from: f. hydrogen atom; g. straight or branched C.sub.1-C.sub.12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; h. straight or branched C.sub.1-C.sub.12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S, i. oligoethers; and j. oligothioethers, provided that R.sub.1 and R.sub.2 are not simultaneously a hydrogen atom, R.sub.3 and R.sub.4, identical or different, occupy the positions left free by R.sub.1 and R.sub.2 and are selected from: k. hydrogen; l. halogens; m. a nitro group; n. a sulphonate group; o. amine groups; p. carbonyl groups; q. mono- or polycyclic aromatic groups; r. straight or branched C.sub.1-C.sub.12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; s. straight or branched C.sub.1-C.sub.12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; and t. oligoethers; with a compound of formula X-Q-X, in which X represents a halogen atom and Q represents a spacer selected from a group consisting of: C.sub.1-C.sub.12 alkylenyl groups, arylenyl groups, oligoethers and oligothioethers.

6. The process according to claim 5, characterized in that in the compound of formula (I), R1 and R2 each represent, independently of one another, a group selected from: i. the phenyl, naphthyl, anthracenyl, indenyl, biphenyl, terphenyl, carbazolyl groups, said groups being able to be substituted by at least one straight or branched C.sub.1-C.sub.12 alkyl group, in particular a methyl group; ii. ##STR00063## groups in which Ra and Rb, identical or different, each represent, independently of one another: a. either a hydrogen atom; b. or a straight or branched C.sub.1-C.sub.12 alkyl group, said alkyl group being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; c. or a straight or branched C.sub.1-C.sub.12 alkoxy group, said alkoxy group being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; d. or an oligoether; e. or an oligothioether.

7. The process according to claim 5, characterized in that in the compound of formula (I), R3 and R4 each represent a hydrogen atom.

8. The process for the synthesis of -conjugated materials according to claim 5 further comprising: a) a step of protecting W when W represents an N(H) group in the compound of formula (II) ##STR00064## and R.sub.3 and R.sub.4, identical or different, are selected from: xii. hydrogen; xiii. halogens; xiv. a nitro group; xv. a sulphonate group; xvi. amine groups; xvii. carbonyl groups; xviii. mono- or polycyclic aromatic groups; xix. straight or branched C.sub.1-C.sub.12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; xx. straight or branched C.sub.1-C.sub.12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; xxi. oligoethers; and xxii. oligothioethers, provided that if R.sub.3 is in position 2 then R.sub.4 is not in position 7 and if R.sub.3 is in position 3 then R.sub.4 is not in position 6, to give a compound of formula (III) ##STR00065## in which GP is an amine protecting group, b) treating the compound of formula (III) with a halogenated derivative, to give a compound of formula (IVb) ##STR00066## in which R.sub.3 and R.sub.4 are as defined in claim 1 and X, in position 3 and 6 of the carbazole represents a halogen atom, in particular an iodine or bromine atom, c) a coupling reaction of said compound of formula (IVb) to give a compound of formula (Vb) ##STR00067## in which R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as defined in claim 5.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The following Examples 1 to 11 and FIGS. 1 and 2 illustrate the invention.

(2) FIG. 1 shows the current-voltage (J-V) curves in the dark of the devices using the semiconductors comprising the compounds 4 to 7 synthesized according to Examples 2 to 5 in combination with the dye D102 according to Example 11.

(3) FIG. 2: Current-voltage (J-V) curves under illumination of the devices using the semiconductors comprising the compounds 4 to 7 synthesized according to Examples 2 to 5 in combination with the dye D102 according to Example 11.

DETAILED DESCRIPTION

EXAMPLE 1

Synthesis of N3,N3,N6,N6,tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine (block 3,6)

(4) It is carried out according to Diagram 1.

(5) ##STR00038##

(6) The first step is protecting the amine in position 9 of the carbazole with a benzyl group according to Estrada, L. A.; Neckers, D. C. Organic Letters 2011, 13, 3304. The second step consists of the iodation of positions 3 and 6 of the carbazole nucleus according to Tucker, S. H. J. Chem. Soc. 1926, 129, 546. In a third step, a CN coupling makes it possible to fix the bis(4-methoxyphenyl)amine group at positions 3 and 6 of the carbazole unit according to Yamamoto, T.; Nishiyama, M.; Koie, Y. Tetrahedron Letters 1998, 39, 2367. The last step is a deprotection reaction making it possible to remove the benzyl group from position 9 of the carbazole nucleus so as to render the amine function available for subsequent use according to Haddach, A. A.; Kelleman, A.; Deaton-Rewolinski, M. V. Tetrahedron letters 2002, 43, 399.

1.1. Synthesis of 9-benzyl-9H-carbazole (1)

(7) Sodium hydride (20 mmol, 0.7 g, 2 eq) is added slowly to a solution of carbazole (10 mmol, 1.7 g, 1 eq) in anhydrous tetrahydrofuran (approximately 30 mL) at ambient temperature. It is noted that a gas is given off (release of H.sub.2) and the solution changes colour from yellow to off-white. The mixture is left under stirring at ambient temperature for one hour, when the solution becomes light brown. Benzyl bromide (1.8 mL, 1.5 eq) is added dropwise to the mixture under stirring at ambient temperature.

(8) The mixture is left under stirring for approximately 3 hours and TLCs are carried out to verify if the reaction has finished. At the end of the reaction, water is added to the reaction mixture which is extracted with diethyl ether. The collected organic phases were dried with MgSO.sub.4 and the solvent is then evaporated. The solid obtained is washed with n-hexane.

(9) The product is obtained in the form of a white solid that is not very dense.

(10) Yield 80%

1.2. Synthesis of 9-benzyl-3,6-diiodo-9H-carbazole (2)

(11) 9-benzyl-9H-carbazole obtained in step 1.1. (16 mmol, 4.1 g, 1 eq) is placed in solution in glacial acetic acid (40-50 mL) in a flask at 80 C. After the 9-benzyl-9H-carbazole has completely dissolved, potassium iodide (KI; 20.8 mmol, 3.5 g, 1.3 eq) and potassium iodate (KIO.sub.3; 12.8 mmol, 2.75 g, 0.8 eq) are then added. The temperature is maintained at 80 C. until the I.sub.2 formed has been completely consumed. Then the mixture is left under stirring at 80 C. until a white precipitate appears. After the precipitate has appeared, TLCs are carried out to verify if the reaction is complete. A 5% sodium thiosulphate solution is then added to the reaction mixture after returning to ambient temperature and the precipitate is recovered by filtration then washed several times with water. The solid obtained is dried.

(12) The product is obtained in the form of a white solid.

(13) Yield: 98%

1.3. 9-benzyl-N3,N3,N6,N6,tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine (3)

(14) Diphenylamine (10 mmol, 2.3 g, 1 eq), diiodine-containing carbazole obtained in step 1.2. (5 mmol, 2.54 g, 0.5 eq), tri-tert-butylphosphine (0.2 mmol, 0.1 mL, 0.2 eq) and palladium acetate (Pd(OAc).sub.2; 0.2 mmol, 5 mg, 0.2 eq) are added to a Schlenk flask. After adapting the bicol with a condenser, the mixture is placed under an argon atmosphere. Toluene (80 mL) is then added to the mixture of reagents. After stirring for 15 minutes at ambient temperature, sodium terbutoxylate (13 mmol, 1.25 g, 1.3 eq) is added to the reaction mixture. After adding the base, the mixture is taken to reflux at 110 C. for one day. TLCs are carried out to verify the end of the reaction. Once the reaction is complete, the crude is filtered with celite. The filtrate obtained is purified by column chromatography (eluent=petroleum ether/ethyl acetate 8:2).

(15) The product is obtained in the form of a yellow powder.

(16) Yield 93%

1.4. N3,N3,N6,N6,Tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine (Block 3,6)

(17) The benzylcarbazole derivative obtained in step 1.3 (2 mmol, 1.45 g, 1 eq) is added to a flask and the medium is then placed under an argon atmosphere. Dimethyl sulphoxide (DMSO) is then added and the reaction mixture is left under stirring at ambient temperature. A 1 M solution of potassium tert-butylate (KOtBu) in THF (12 mmol, 1.4 g, 6 eq i.e. 12 mL of a 1 M solution of KO-Bu in THF) is then added to the mixture. The argon stream is stopped and dioxygen is bubbled through the reaction medium which remains under stirring at ambient temperature for approximately 3 hours. TLCs are carried out to monitor the progress of the reaction. At the end of the reaction, water is added to the reaction mixture and the crude is extracted with acetate. The organic phase is washed with a saturated solution of NaHCO.sub.3 to remove the benzoic acid formed, then with saline solution. The organic phase is then dried with MgSO.sub.4 and the solvent is evaporated. After purification by column chromatography (eluent=petroleum ether/ethyl acetate 7:3) the product is obtained in the form of a light yellow powder.

(18) Yield: 80%

EXAMPLE 2

Synthesis of 9,9-(1,4-phenylene)bis(N3, N3,N6,N6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine) (Compound 4)

(19) ##STR00039##
N.sup.3,N.sup.3,N.sup.6,N.sup.6,tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine (block 3,6) prepared in Example 1 (0.48 mmol, 300 mg, 1 eq), 4,4 diiodophenyle (0.24 mmol, 81 mg, 0.5 eq), potassium carbonate (K2CO.sub.3; 3.84 mmol, 540 mg, 8 eq), copper (1.92 mmol, 120 mg, 4 eq) and 18-crown-6 ether (0.03 mmol, 10 mg, 0.06 eq) are added to a microwave reaction tube. After placing the tube containing the reagents under an inert atmosphere, 3 to 5 ml of ortho-dichlorobenzene is added. The reaction medium is heated by microwave at 210 C. for approximately 1 hour. TLCs were carried out to monitor the progress of the reaction and at the end of the reaction, the reaction mixture is filtered to remove the remaining inorganic reagents. The filtrate obtained is concentrated in an evaporator (by evaporating a part of ortho-dichlorobenzene).

(20) The crude product obtained is purified by precipitation from acetone to obtain a pale green solid.

(21) Yield 50%

EXAMPLE 3

Synthesis of 9,9-([1,1-biphenyl]-4,4-diyl)bis(N3,N3,N6,N6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine) (Compound 5)

(22) ##STR00040##

(23) The block [3,6] prepared in Example 1 (0.48 mmol, 300 mg, 1 eq), 4,4-diiodobiphenyl (0.24 mmol, 98 mg, 0.5 eq), potassium carbonate (K.sub.2CO.sub.3; 3.84 mmol, 540 mg, 8 eq), copper (1.92 mmol, 120 mg, 4 eq) and 18-crown-6 ether (0.03 mmol, 10 mg, 0.06 eq) are added to a microwave reaction tube. After placing the tube containing the reagents under an inert atmosphere, 3 to 5 ml of ortho-dichlorobenzene is added. The reaction medium is heated by microwave at 210 C. for approximately 1 hour. TLCs were carried out to monitor the progress of the reaction. At the end of the reaction, the reaction mixture is filtered to remove the remaining inorganic reagents. The filtrate obtained was concentrated in an evaporator (by evaporating a part of ortho-dichlorobenzene). The crude product obtained is purified by precipitation from acetone to obtain a pale green solid.

(24) Yield: 43%

EXAMPLE 4

Synthesis of 9,9-(9,9-dihexyl-9H-fluorene-2,7-diyl)bis(N3,N3,N6,N6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine) (Compound 7)

(25) ##STR00041##

4.1. Synthesis of 9,9-dihexyl-2,7-diiodo-9H-fluorene

4.1.1. Synthesis of 2,7-diiodo-9H-fluorene

(26) Fluorene (4 g, 24 mmol, 1 eq) is placed in solution in a mixture containing acetic acid (60 mL), water (13 mL) and sulphuric acid (2 mL) at 95 C. After reducing the temperature to 80 C., diiodine (4.2 g, 16.6 mmol, 0.7 eq) and periodic acid (1.85, 8 mmol, 0.33 eq) are then added to the reaction mixture, which is then left under stirring for approximately 1 hour. TLCs were carried out to monitor the progress of the reaction. The precipitate formed was recovered by filtration then washed with a saturated solution of NaHCO.sub.3 and water. The crude solid obtained was recrystallized in n-hexane.

(27) The product is obtained in the form of a white solid.

(28) Yield: 50%

4.1.2. Synthesis of 9,9-dihexyl-2,7-diiodo-9H-1-fluorene

(29) The diiodine-containing fluorene obtained in the preceding step, (4.2 g, 10 mmol, 1 eq), n-bromo-hexane (3.63 g, 22 mmol, 2.2 eq) and potassium tert-butoxide (3.36 g, 30 mmol, 3 eq) are placed in solution in anhydrous THF (30 mL) in a flask. After placing the medium under an inert atmosphere under argon, the reaction mixture is taken to 40 C. then left under stirring overnight. TLCs were carried out to monitor the progress of the reaction. At the end of the reaction, the reaction mixture is allowed to return to ambient temperature, then poured into cold water. The crude product obtained was extracted with diethyl ether, the collected organic phases were washed with saline solution then dried with MgSO.sub.4. After evaporation of the solvent, the crude product was purified by column chromatography with the eluent petroleum ether/ethyl acetate (9.5:0.5).

(30) The product is obtained in the form of a white solid.

(31) Yield: 78%

4.2. Synthesis of 9,9-(9,9-dihexyl-9H-fluorene-2,7-diyl)bis(N3,N3,N6,N6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine)

(32) The block [3,6] prepared in Example 1 (0.48 mmol, 300 mg, 1 eq), the diiodine-containing fluorene derivative prepared in the preceding step (0.24 mmol, 141 mg, 0.5 eq), potassium carbonate (3.84 mmol, 540 mg, 8 eq), copper (1.92 mmol, 120 mg, 4 eq) and 18-crown-6 ether (0.03 mmol, 10 mg, 0.06 eq) were added to a microwave reaction tube. After placing the tube containing the reagents under an inert atmosphere, 3 to 5 ml of ortho-dichlorobenzene is added. The reaction medium is heated by microwave at 210 C. for 2 hours approximately. TLCs were carried out to monitor the progress of the reaction. At the end of the reaction, the reaction mixture is filtered to remove the remaining the inorganic reagents. The filtrate obtained was concentrated in an evaporator (by evaporating a part of ortho-dichlorobenzene). The crude product obtained is purified by column chromatography using the eluent: petroleum ether/ethyl acetate 7:3.

(33) The product is obtained in the form of a light yellow powder.

(34) Yield: 44%

EXAMPLE 5

Synthesis of 9,9-(((((oxybis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl))bis(4,1-phenylene))bis(N3,N3,N6,N6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine) (Compound 6)

(35) ##STR00042##

5.1. Synthesis of 4,4-((((oxybis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl))bis(oxy))bis(iodobenzene)

5.1.1. Synthesis of ((oxybis(ethane-2,1-diyl)bis(oxy))bis(ethane-2,1-diyl))bis(4-methythenzenesulphonate) or ethylene glycol ditosylate

(36) Glycol ether (10 mmol, 1 eq) is placed in solution in tetrahydrofuran (20 mL) in a flask, tosyl chloride (25 mmol, 2.5 eq) is then added and an aqueous solution of potassium hydroxide (4 ml, 16 M, 64 mmol, 6.4 eq) is then added dropwise to the reaction mixture. After stirring for approximately 7 hours at ambient temperature, TLCs were carried out to monitor the progress of the reaction. At the end of the reaction, the reaction mixture is poured into a solution of cold water and the precipitate formed is recovered by filtration.

(37) The product is obtained in the form of a white solid

(38) Yield: 85%

5.1.2. Synthesis of 4,4-((((oxybis(ethane-2,1-diyl)bis(oxy))bis(ethane-2,1-diyl))bis(oxy))bis(iodobenzene)

(39) A solution of iodophenol (3.8 g, 17 mmol, 1 eq) is placed in solution in dimethylformamide (60 mL) in a flask, and potassium tert-butylate (2.9 g, 26 mmol, 1.5 eq) is then added slowly. The glycol ether ditosylate derivative obtained in the preceding step (4.3 g, 8.5 mmol, 0.5 eq) is then added to the reaction mixture which is left under stirring overnight at ambient temperature. During the addition of the ditosylate, the formation of a white precipitate is noted. TLCs were carried out to monitor the progress of the reaction. At the end of the reaction, water is added to the reaction mixture. The crude product obtained is then extracted with ethyl acetate and the collected organic phases are washed with a saturated NaHCO.sub.3 solution and dried with MgSO.sub.4.

(40) The product is obtained in the form of a white solid.

(41) Yield: 95%

5.2. Synthesis of 9,9-(((((oxybis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl))bis(4,1-phenylene))bis(N3,N3, N6, N6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine)

(42) The block [3,6] prepared in Example 1 (0.48 mmol, 300 mg, 1 eq), the diiodine-containing ethylene glycol derivative prepared in the preceding step (0.24 mmol, 98 mg, 0.5 eq), potassium carbonate (3,84 mmol, 540 mg, 8 eq), copper (1.92 mmol, 120 mg, 4 eq) and 18-crown-6 ether (0.03 mmol, 10 mg, 0.06 eq) are added. After placing the tube containing the reagents under an inert atmosphere, 3 to 5 ml of ortho-dichlorobenzene are added. The reaction medium is heated by microwave at 210 C. during 1 hour approximately. TLCs were carried out to monitor the progress of the reaction. At the end of the reaction, the reaction mixture is filtered to remove the remaining the inorganic reagents. The filtrate obtained was concentrated in an evaporator (by evaporating a part of ortho-dichlorobenzene). The crude product obtained is purified by column chromatography using the eluent: petroleum ether/ethyl acetate 7:3.

(43) The product is obtained in the form of a green powder.

(44) Yield: 45%.

EXAMPLE 6

Synthesis of N3,N3,N6,N6,Tetrakis(4-methoxyphenyl)-9-(2-naphthalene)-carbazole-3,6-diamine (compound A), of N3,N3,N6,N6,tetrakis(4-methoxyphenyl)-9-(1-pyrene)-carbazole-3,6-diamine (compound B) and of N3,N3,N6,N6,tetrakis(4-methoxyphenyl)-9-(4-fluorobenzene)-carbazole-3,6-diamine (Compound C)

(45) ##STR00043##
Obtaining Compound A:

(46) The synthon N.sup.3,N.sup.3,N.sup.6,N.sup.5,tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine (block 3,6) obtained in Example 1 (1 g, 1 eq), NaOtBu (7 eq), 2-bromonaphthalene (1.1 eq) then Pd(OAc).sub.2 (10%), tri-tert-butylphosphine (20%) as well as toluene (2 ml) are added to a microwave tube under a controlled atmosphere. The solution is heated by microwave at 200 C. for 20 min then, in an oil bath to reflux for 48 hours. The solution is filtered over celite then purified by column chromatography over silica gel. The yield is 87%.

(47) Obtaining Compounds B and C:

(48) Compounds B and C are obtained according to the same protocol, using 1-bromopyrene or 1-fluoro-4-iodobenzene respectively.

(49) The yields obtained for compounds B and C are 83% and 91% respectively.

EXAMPLE 7

Synthesis of 9,9-(9-dodecanyl-9H-carbazole-3,6-diyl)bis(N3,N3,N6,N6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine)) (Compound 8)

(50) ##STR00044##

(51) The synthon N.sup.3,N.sup.3,N.sup.6,N.sup.6,tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine (block 3,6) obtained in Example 1 (1 g, 1 eq), NaOtBu (7 eq), 3,6-dibromo-9-dodecylcarbazole (0.5 eq) then Pd(OAc).sub.2 (10%), tri-tert-butylphosphine (20%) as well as toluene (2 ml) are added to a microwave tube under a controlled atmosphere. The solution is heated by microwave at 200 C. for 20 min, then in an oil bath to reflux for 48 hours. The solution is filtered over celite then purified by column chromatography over silica gel.

(52) The yield is 35%.

EXAMPLE 8

Synthesis of 9,9-(propyl) bis(N3,N3,N6,N6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine) (Compound 9)

(53) ##STR00045##

(54) The synthon N.sup.3,N.sup.3,N.sup.6,N.sup.6,tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine (block 3,6) obtained in Example 1 (1 g, 2.1 eq) and NaH (4 eq) are placed in solution in 10 mL of DMF in a 100 ml Schlenk flask. The mixture is left under stirring at ambient temperature for one hour. 1,3-dibromopropane (1 eq) is added dropwise and the solution is stirred overnight. The reaction is quenched with 5 mL of MeOH. After evaporation of the solvent, the precipitate is solubilized in CHCl.sub.3. The organic phase is washed then dried over MgSO.sub.4. The reaction crude is purified by column chromatography over silica gel with a solvent mixture: petroleum ether/ethyl acetate. The yield is 35%.

EXAMPLE 9

Synthesis of 9,9-(hexyl) bis(N3,N3,N6,N6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine) (Compound 10)

(55) ##STR00046##

(56) Compound 10 was obtained according to the same protocol as that used in Example 8, using 1,6 dibromohexane respectively.

(57) The yield obtained for the compound is 60%.

EXAMPLE 10

Synthesis of 9,9-(dodecyl) bis(N3,N3,N6,N6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine) (Compound 11)

(58) ##STR00047##

(59) The compound 11 was obtained according to the same protocol as that used in Example 8, using 1,12 dibromododecane respectively.

(60) The yield obtained for the compound is 84%.

EXAMPLE 11

Efficiency of the Molecular Glasses of Examples 2 to 5 as Organic Semiconductors in the ssDSSC Devices

(61) The development of dye-sensitized solid-state photovoltaic cells takes place in several steps. It starts with the preparation of the tin oxide-doped fluorine substrate (SnO.sub.2: F or FTC) and finishes with the deposition of the gold or silver electrode. The different steps of this manufacturing process will be described successively.

(62) Manufacture of the All-solid-state DSSC Photovoltaic Devices.

(63) The four molecular glasses: Compound 4: 9,9-(1,4-phenylene)bis(N.sup.3,N.sup.3,N.sup.6,N.sup.6,tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine), (obtained according to the process of Example 2); Compound 5: 9,9-([1,1-biphenyl]-4,4-diyl)bis(N.sup.3,N.sup.3,N.sup.6,N.sup.6,tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine), (obtained according to the process of Example 3); Compound 6: 9,9-(((((oxybis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl))bis(4,1-phenylene))bis(N.sup.3,N.sup.3,N.sup.6,N.sup.6,tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine), (obtained according to the process of Example 5); Compound 7: 9,9-(9,9-dihexyl-9H-fluorene-2,7-diyl)bis(N.sup.3,N.sup.3,N.sup.6,N.sup.6, tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine), (obtained according to the process of Example 4),
were used as organic semiconductors for the DSSC devices in combination with the dye D102 which is a commercial product, the chemical structure of which is presented below.

(64) ##STR00048##

(65) The manufacture of all-solid-state DSSC photovoltaic devices (ssDSSC) was carried out according to the protocol well known to a person skilled in the art and in particular described in the publication by Puckyte et al (Carbazole-based molecular glasses for efficient solid-state dye-sensitized solar cells, Journal of Power Sources, 2013, vol 233, p86-92). The measurements of the performances of the devices are carried out in the dark and under illumination (AM 1.5 G). The composition of the cell is as follows: FTO/TiO.sub.2/D102/HTM/Ag. The semiconductors are represented by the hole transporting materials (HTMs). The solutions used for the development of the hole transporting layer have a HTM concentration of 200 mg/mL in chlorobenzene, in the presence of additives commonly used for DSSCs, namely lithium bis(trifluoromethane)sulphonimide (LiTFSI) and 4-tertbutylpyridine. The results obtained are presented in FIGS. 1 and 2 and summarized in Table 1 below.

(66) TABLE-US-00001 TABLE 1 Photovoltaic parameters of the devices using HTMs comprising compounds 4, 5, 6 and 7 in combination with the dye D102 (in the dark and under illumination) Glasses J.sub.SC (mA .Math. cm2) V.sub.OC (V) FF (%) Yield (%) Compound 4 4.17 0.75 43 1.34 Compound 5 7.45 0.73 43 2.36 Compound 6 4.31 0.79 59 2.03 Compound 7 4.33 0.82 46 1.63 Definitions of the abbreviations used in Table 1: Jsc: short-circuit current density (mA .Math. cm.sup.2) Voc: open-circuit voltage (V) FF: form factor (%)

CONCLUSION

(67) The characteristics were obtained in the dark and under illumination (AM 1.5 G). The four devices show a diode characteristic in the dark and a photovoltaic effect under illumination via the appearance of a photogenerated current (see FIGS. 1 et 2). The short-circuit current densities obtained are situated between 4.17 mA.Math.cm.sup.2 and 7.45 mA.Math.cm.sup.2 and the open-circuit voltage values are comprised between 0.73 V and 0.82 V. The photovoltaic conversion efficiencies range from 1.34% to 2.36%. Compound 5 is the one which allowed the best conversion efficiency to be obtained, which is 2.36%.