Organic photochromic dye and uses thereof for dye sensitized solar cells

Abstract

The present invention concerns an organic dye comprising a photochromic entity, a segment -eD representing an electron donor segment and a segment -L-A with -L- representing a covalent bond or a spacer segment and particularly a pi-conjugated spacer segment, and -A representing an electron attractor segment able to form a covalent bond with a semi-conductor. The present invention concerns the use thereof as photosensitizer in a photovoltaic device and said photovoltaic device.

Claims

1. An organic dye of formula (I): ##STR00052## wherein Ar.sub.1 and Ar.sub.2 are independently an optionally substituted aryl group, R.sub.1 to R.sub.4 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, or an optionally substituted arylalkyl group, R.sub.1 and R.sub.2 optionally forming with the carbons to which they are attached an optionally substituted aromatic or heteroaromatic ring, and R.sub.3 and R.sub.4 optionally forming with the carbons to which they are attached an optionally substituted aromatic or heteroaromatic, wherein Ar.sub.1 and/or Ar.sub.2 is substituted by -eD and at least one selected from the group consisting of R.sub.1, R.sub.2, R.sub.3, R.sub.4, the aromatic or heteroaromatic ring formed by R.sub.1 and R.sub.2 with the carbons to which they are attached, and the aromatic or heteroaromatic ring formed by R.sub.3 and R.sub.4 with the carbons to which they are attached, is substituted by -L-A, or wherein Ar.sub.1 and/or Ar.sub.2 is substituted by -L-A and at least one selected from the group consisting of R.sub.1, R.sub.2, R.sub.3, R.sub.4, the aromatic or heteroaromatic ring formed by R.sub.1 and R.sub.2 with the carbons to which they are attached, and the aromatic or heteroaromatic ring formed by R.sub.3 and R.sub.4 with the carbons to which they are attached, is substituted by -eD, or wherein Ar.sub.1 and/or Ar.sub.2 is substituted by -eD and at least one selected from the group consisting of R.sub.3, R.sub.4, R.sub.15, R.sub.16, R.sub.17, R.sub.18, and the aromatic or heteroaromatic ring formed by R.sub.17 and R.sub.18 with the carbons to which they are attached is substituted by -L-A; or wherein Ar.sub.1 and/or Ar.sub.2 is substituted by -L-A and at least one selected from the group consisting of R.sub.3, R.sub.4, R.sub.15, R.sub.16, R.sub.17, R.sub.18, and the aromatic or heteroaromatic ring formed by R.sub.17, and R.sub.18 with the carbons to which they are attached is substituted by -eD wherein -eD is electron donor segment that is an amino group of a formula, (Z.sub.1)(Z.sub.2)N—, with Z.sub.1 and Z.sub.2 independently being an optionally substituted alkyl group or an optionally substituted aryl group, -L- is a covalent bond or a spacer segment, and -A is an electron attractor segment, able to form a covalent bond with a semi-conductor, that is a carboxylic acid group, a cyanoacrylic acid group, a phosphonic group, a dithiocarbonic group, or a group of formula: ##STR00053## and wherein, if R.sub.1 and R.sub.2 form a ring of formula (VIa) ##STR00054## R.sub.15 to R.sub.18 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, or an optionally substituted arylalkyl group, R.sub.15 and R.sub.16 optionally forming together a ═O or ═C(R.sub.24)(R.sub.25) group with R.sub.24 and R.sub.25 independently being a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, or an optionally substituted arylalkyl group, and R.sub.17 and R.sub.18 optionally forming with the carbons to which they are attached an optionally substituted aromatic or heteroaromatic ring.

2. The dye of claim 1, having a formula (III): ##STR00055## wherein R.sub.3 and R.sub.4 are as defined in claim 1, R.sub.5 to R.sub.8 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (˜NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, an optionally substituted arylalkyl group, -eD, or -L-A, R.sub.9 and R.sub.10 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, an optionally substituted arylalkyl group, -eD, or -L-A, wherein R.sub.9 and/or R.sub.10 is -eD or is substituted by -eD and at least one selected from the group consisting of R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 is -L-A or substituted by -L-A, or wherein R.sub.9 and/or R.sub.10 is -L-A or is substituted by -L-A and at least one selected from the group consisting of radical R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.7, and R.sub.8 is -eD or is substituted -eD, -eD and -L-A being as defined in claim 1.

3. The dye of claim 1, having formula (V): ##STR00056## wherein R.sub.1 and R.sub.2 are as defined in claim 1, R.sub.9 and R.sub.10 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, an optionally substituted arylalkyl group, -eD, or a -L-A, R.sub.11 to R.sub.14 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, an optionally substituted arylalkyl group, -eD, or L-A, R.sub.11 and R.sub.12 optionally forming with the carbons to which they are attached an optionally substituted aromatic or heteroaromatic ring, and R.sub.13 and R.sub.14 optionally forming with the carbons to which they are attached an optionally substituted aromatic or heteroaromatic ring, wherein R.sub.9 and/or R.sub.10 is -eD or is substituted by -eD and at least one selected from group consisting of R.sub.1, R.sub.2, R.sub.11, R.sub.12, R.sub.13, R.sub.14, the aromatic or heteroaromatic ring formed by R.sub.11 and R.sub.12 with the carbons to which they are attached, and the aromatic or heteroaromatic ring formed by R.sub.13 and R.sub.14 with the carbons to which they are attached, is -L-A or is substituted by -L-A, or wherein R.sub.9 and/or R.sub.10 is -L-A or is substituted by -L-A and at least one selected from the group consisting of R.sub.1, R.sub.2, R.sub.11, R.sub.12, R.sub.13, R.sub.14, the aromatic or heteroaromatic ring formed by R.sub.11 and R.sub.12 with the carbons to which they are attached, and the aromatic or heteroaromatic ring formed by R.sub.13 and R.sub.14 with the carbons to which they are attached, is -eD or is substituted by -eD, -eD and -L-A being as defined in claim 1.

4. The dye of claim 1, wherein -L- is a pi-conjugated function.

5. The dye of claim 1, having a structure ##STR00057## ##STR00058## ##STR00059##

6. The dye of claim 1, having a structure ##STR00060##

7. The dye of claim 1, having a structure ##STR00061##

8. The dye of claim 1, having a structure ##STR00062##

9. The dye of claim 1, having a structure ##STR00063##

10. The dye of claim 1, having a structure ##STR00064##

11. The dye of claim 1, having a structure ##STR00065##

12. The dye of claim 1, having a structure ##STR00066##

13. A process, comprising: photosensitizing a photovoltaic device with the dye of claim 1.

14. A photovoltaic device, comprising: a nanostructured semi-conductor metal oxide layer comprising the dye of claim 1, the dye sensitizing the layer.

15. The device of claim 14, comprising: an anode; and a counter electrode, wherein the anode and counter electrode are separated from each other by an electrolyte and optionally one or more polymer shims.

16. The device of claim 14, wherein the semi-conductor metal oxide is a binary, tertiary, or quaternary metal oxide

17. The device of claim 15, wherein the nanostructured semi-conductor metal oxide layer is in the form of a mesoporous layer and is deposited on the anode.

18. The device of claim 15, wherein the electrolyte is a liquid, an ionic liquid, a gel, or a solid.

19. An organic dye of formula (VIII): ##STR00067## wherein R.sub.9 and R.sub.10 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, an optionally substituted arylalkyl group, -eD, or -L-A, -eD is an electron donor segment that is an amino group of a formula, (Z.sub.1)(Z.sub.2)N—, with Z.sub.1 and Z.sub.2 independently being an optionally substituted alkyl group or an optionally substituted aryl group, -L- is a covalent bond or a spacer segment, and -A is an electron attractor segment, able to form a covalent bond with a semi-conductor, that is a carboxylic acid group, a cyanoacrylic acid group, a phosphonic group, a dithiocarbonic group, or a group of formula: ##STR00068## R.sub.11 to R.sub.14 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, an optionally substituted arylalkyl group -eD, or -L-A, R.sub.11 and R.sub.12 optionally forming with the carbons to which they are attached an optionally substituted aromatic or heteroaromatic ring, and R.sub.13 and R.sub.14 optionally forming with the carbons to which they are attached an optionally substituted aromatic or heteroaromatic ring, X is C(R.sub.26) or N; R.sub.15 and R.sub.16 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, or an optionally substituted arylalkyl group, R.sub.15 and R.sub.16 optionally forming together a ═O or ═C(R.sub.24)(R.sub.25) group with R.sub.24 and R.sub.25 independently being a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, or an optionally substituted arylalkyl group, R.sub.19 to R.sub.21 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, an optionally substituted arylalkyl group -eD, or -L-A, R.sub.26 is a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, or optionally substituted an arylalkyl group, wherein R.sub.9 and/or R.sub.10 is -eD or is substituted by -eD and at least one selected from group consisting of R.sub.11, R.sub.12, R.sub.13, R.sub.14, the aromatic or heteroaromatic ring formed by R.sub.11 and R.sub.12 with the carbons to which they are attached, the aromatic or heteroaromatic ring formed by R.sub.13 and R.sub.14 with the carbons to which they are attached, R.sub.15, R.sub.16, R.sub.19, R.sub.20, R.sub.21, R.sub.24, and R.sub.25, is -L-A or is substituted by -L-A, or wherein R.sub.9 and/or R.sub.10 is -L-A or is substituted by -L-A and at least one selected from the group consisting of R.sub.11, R.sub.12, R.sub.13, R.sub.14, the aromatic or heteroaromatic ring formed by R.sub.11 and R.sub.12 with the carbons to which they are attached, the aromatic or heteroaromatic ring formed by R.sub.13 and R.sub.14 with the carbons to which they are attached, R.sub.15, R.sub.16, R.sub.19, R.sub.20, R.sub.21, R.sub.24, and R.sub.25, is -eD or is substituted by -eD.

20. An organic dye of formula (X): ##STR00069## wherein R.sub.9 and R.sub.10 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, an optionally substituted arylalkyl group, -eD or -L-A, -eD is an electron donor segment that is an amino group of a formula, (Z.sub.1)(Z.sub.2)N—, with Z.sub.1 and Z.sub.2 independently being an optionally substituted alkyl group or an optionally substituted aryl group, -L- is a covalent bond or a spacer segment, and -A is an electron attractor segment, able to form a covalent bond with a semi-conductor, that is a carboxylic acid group, a cyanoacrylic acid group, a phosphonic group, a dithiocarbonic group, or a group of formula: ##STR00070## R.sub.11 to R.sub.14 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, an optionally substituted arylalkyl group, -eD, or -L-A, R.sub.11 and R.sub.12 optionally forming with the carbons to which they are attached an optionally substituted aromatic or heteroaromatic ring, and R.sub.13 and R.sub.14 optionally forming with the carbons to which they are attached an optionally substituted aromatic or heteroaromatic ring, R.sub.15 and R.sub.16 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, or an optionally substituted arylalkyl group, R.sub.15 and R.sub.16 optionally forming together a ═O or ═C(R.sub.24)(R.sub.25) group with R.sub.24 and R.sub.25 independently being a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, or an optionally substituted arylalkyl group, Y is C(R.sub.27)(R.sub.28), C(═O), S, Se, O, N(R.sub.29), P(R.sub.30), or Si(R.sub.31)(R.sub.32); R.sub.22 and R.sub.23 are independently a hydrogen, a halogen, a cyano group (—CN), a nitro group (—NO.sub.2), an optionally substituted alkyl group, an optionally substituted aryl group an optionally substituted alkylaryl group, an optionally substituted arylalkyl group, -eD, or -L-A, R.sub.27 to R.sub.32 are independently a hydrogen, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylaryl group, or an optionally substituted arylalkyl group, wherein R.sub.9 and/or R.sub.10 is -eD or is substituted by -eD and at least one selected from the group consisting of R.sub.11, R.sub.12, R.sub.13, R.sub.14, the aromatic or heteroaromatic ring formed by R.sub.11 and R.sub.12 with the carbons to which they are attached, the aromatic or heteroaromatic ring formed by R.sub.13 and R.sub.14 with the carbons to which they are attached, R.sub.15, R.sub.16, R.sub.22, R.sub.23, R.sub.24, and R.sub.25, is -L-A or is substituted by -L-A, or wherein R.sub.9 and/or R.sub.10 is -L-A or is substituted by -L-A and at least one selected from the group consisting of R.sub.11, R.sub.12, R.sub.13, R.sub.14, the aromatic or heteroaromatic ring formed by R.sub.11 and R.sub.12 with the carbons to which they are attached, the aromatic or heteroaromatic ring formed by R.sub.13 and R.sub.14 with the carbons to which they are attached, R.sub.15, R.sub.16, R.sub.22, R.sub.26, R.sub.24, and R.sub.25, is a -eD or is substituted by -eD.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the absorption spectrum of two organic chromophoric dyes according to the present invention (DJ277 and YKC5P21).

(2) FIG. 2 presents photographs of a solar cell the photosensitizer of which is the organic chromophoric dye according to the present invention (YKCP5P21) at different light irradiation power with Low light=0.1 Sun, Medium Light=0.3 Sun, Full power=1 Sun and 1 Sun=1000 W/m.sup.2.

DETAILED DISCUSSION OF PARTICULAR EMBODIMENTS

I. Synthesis of the Compounds

I.1. Nuclear Magnetic Resonance (NMR)

(3) NMR spectra were recorded on Bruker AC 200 MHz and Bruker AC 400 MHz spectrometers. The deuterated solvents used were chloroform-d (1H, δ: 7.26, 13C, δ: 77.16), acetone-d.sub.6 (1H δ: 2.05, 13C, δ: 29.84), tetrahydrofuran-d.sub.8 (1H, δ: 3.58, 13C, δ: 67.21) and dichloromethane-d.sub.2 (1H, δ: 5.32, 13C, δ: 53.84). The follow abbreviations were used: s for singlet, d for doublet, t for triplet, m for multiplet and br for broaden signals.

(4) All synthesis intermediates and final products were characterized by .sup.1H and .sup.13C NMR to confirm their structures.

I.2. Synthesis of (Z)-2-cyano-3-(4-(8-(diphenylamino)-3-phenyl-3H-benzo[f]chromen-3-yl)phenyl)acrylic acid (DJ254)

A. 1-(4-bromophenyl)-1-phenylprop-2-yn-1-ol

(5) ##STR00015##

(6) Under argon, sodium acetylide (3.68 g, 76.6 mmol, 18 wt % in xylene) was dissolved in anhydrous THF. 4-bromobenzophenone (2.00 g, 7.6 mmol) was added in one portion at 0° C. After reaching room temperature the reaction mixture was stirred for 3 h. Then an ammonium chloride (NH.sub.4Cl) saturated solution was added to the reaction and stirred for 10 min. The organic phase was extracted with diethyl ether (Et.sub.2O), dried on sodium sulfate and concentrated. Purification on silica gel using dichloromethane (DCM) as eluent to give a pale yellow solid (1.75 g, 6.1 mmol, 80%).

(7) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=7.63-7.58 (m, 2H, H.sub.ar), 7.49 (qAB, 4H, J Δvab=9.1 Hz, J=8.6 Hz, H.sub.ar), 7.40-7.27 (m, 3H, H.sub.ar), 3.11 (s, 1H, OH), 2.97 (s, 1H, C≡CH).

(8) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=144.19, 143.87, 131.35, 128.41, 128.06, 127.80, 125.82, 121.81, 85.78, 75.87, 73.81.

B. 6-(diphenylamino)naphthalen-2-ol

(9) ##STR00016##

(10) Under air condition, 2-bromo-6-naphtol (1.00 g, 4.5 mmol), 4-diphenylamine (834 mg, 5.0 mmol), Tris(dibenzylideneacetone)dipalladium(0) (Pd.sub.2dba.sub.3, 82 mg, 89 μmol), Tri-tert-butylphosphonium tetrafluoroborate (HP.sup.tBu.sub.3BF.sub.4, 52 mg, 179 μmol) and potassium tert-butoxide (.sup.tBuOK, 1.5 g, 13.5 mmol) were dissolved in anhydrous toluene. The mixture was refluxed for 36 hours before being cooled to room temperature and poured into a HCl (2 M) solution. The organic phase was extracted with DCM, dried on sodium sulfate and concentrated. Purification on silica gel using n-hexane/ethyl acetate (EtOAc) (8:2) as eluent to give a white solid (0.97 g, 3.2 mmol, 70%).

(11) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=7.60 (d, 1H, J=8.8 Hz, H.sub.ar), 7.52 (d, 1H, J=8.8 Hz, H.sub.ar), 7.25 (d, 1H, J=2.1 Hz, H.sub.ar), 7.30-7.20 (m, 5H, H.sub.ar), 7.13-7.06 (m, 4H, H.sub.ar), 7.05-6.98 (m, 3H, H.sub.ar), 5.05 (s, 1H, OH).

(12) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=152.80, 147.97, 143.57, 131.31, 129.75, 129.18, 128.74, 127.32, 125.59, 123.86, 122.55, 121.31, 117.98, 109.34.

C. 3-(4-bromophenyl)-N,N,3-triphenyl-3H-benzo[f]chromen-8-amine

(13) ##STR00017##

(14) Under argon, 1-(4-bromophenyl)-1-phenylprop-2-yn-1-ol (691.0 mg, 2.41 mmol), 6-(diphenylamino)naphthalen-2-ol (500.0 mg, 1.61 mmol), pyridinium p-toluenesulfonate (PPTS, 20 mg, 80 μmol) were dissolved in anhydrous chloroform. Trimethyl orthoformate (0.35 mL, 3.21 mmol) was added and the reaction was heated to reflux for 9 h. Solvent was removed under reduced pressure and the crude solid was purified on silica gel using n-hexane/DCM (7:3) as eluent to give a white solid (628 mg, 1.08 mmol, 67%).

(15) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=7.90 (d, 1H, J=9.1 Hz), 7.53-7.46 (m, 5H, H.sub.ar, CH═), 7.45-7.40 (m, 2H, H.sub.ar), 7.40-7.25 (m, 10H, H.sub.ar), 7.16 (d, 1H, J=8.9 Hz), 7.13-7.08 (m, 4H, H.sub.ar), 7.05 (tt, 2H, J=7.3 Hz, J=1.1 Hz, H.sub.ar), 6.31 (d, 1H, J=9.9 Hz, CCH═).

(16) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=149.48, 147.83, 144.38, 144.07, 143.89, 131.16, 130.45, 129.22, 128.91, 128.76, 128.18, 127.69, 126.78, 126.20, 125.55, 123.98, 122.71, 122.48, 121.64, 121.53, 120.19, 118.47, 114.46, 81.91.

D. 4-(8-(diphenylamino)-3-phenyl-3H-benzo[f]chromen-3-yl)benzaldehyde

(17) ##STR00018##

(18) Under argon, 3-(4-bromophenyl)-N,N,3-triphenyl-3H-benzo[f]chromen-8-amine (200 mg, 0.34 mmol) was dissolved in distilled THF. Then n-Butyllithium (n-BuLi, 1.1 M, 0.34 mL, 0.38 mmol) was added at −78° C. The reaction was stirred at temperature ranging from −80° C. to −60° C. for 1 h before adding Dimethylformamide (DMF, 50 μL, 0.69 mmol) at −78° C. The reaction was allowed to reach room temperature and stirred for 12 h and then quenched with water. The organic phase was recovered with EtOAc, dried on sodium sulfate and concentrated under reduced pressure. The crude product was purified on silica gel using DCM/petroleum ether (9:1) as eluent to give a yellow solid (85 mg, 0.16 mmol, 46%).

(19) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=9.97 (s, 1H, CHO), 7.87 (d, 1H, J=9.1 Hz), 7.77 (qAB, 4H, J Δvab=52.3 Hz, J=8.3 Hz, H.sub.ar), 7.53-7.47 (m, 2H, CH═, H.sub.ar), 7.45 (d, 1H, J=8.9 Hz), 7.38-7.21 (m, 10H, H.sub.ar), 7.16 (d, 1H, J=8.8 Hz), 7.10-7.04 (m, 4H, H.sub.ar), 7.02 (tt, 2H, J=7.3 Hz, J=1.1 Hz, H.sub.ar), 6.33 (d, 1H, J=9.9 Hz, CCH═).

(20) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=191.63, 151.41, 149.45, 147.81, 144.06, 143.97, 135.65, 130.51, 129.41, 129.24, 129.03, 128.29, 127.88, 127.37, 126.86, 126.18, 125.57, 124.02, 122.76, 122.50, 121.88, 121.56, 120.55, 118.45, 114.49, 82.06.

E. (Z)-2-cyano-3-(4-(8-(diphenylamino)-3-phenyl-3H-benzo[f]chromen-3-yl)phenyl)acrylic acid (DJ254)

(21) ##STR00019##

(22) 4-(8-(diphenylamino)-3-phenyl-3H-benzo[f]chromen-3-yl)benzaldehyde (105 mg, 0.20 mmol), cyanoacetic acid (73 mg, 0.99 mmol), were dissolved in a mixture of acetonitrile (8 mL) and chloroform (5 mL). A catalytic amount of piperidine was added and the solution was refluxed for 3 h. Solvent was removed under reduced pressure and the solid dissolved in chloroform. The organic phase was washed with a HCl solution (2 M), dried on sodium sulfate (Na.sub.2SO.sub.4) and concentrated. The crude solid was chromatographed on silica using DCM followed by DCM/methanol (MeOH) and DCM/MeOH/Acetic acid 96/2/2 as eluents to afford pale yellow solid (75 mg, 0.13 mmol, 63%).

(23) .sup.1H RMN (THF-ds, 400 MHz): δ=8.25 (s, 1H, CH═), 7.98 (d, 1H, J=9.1 Hz, H.sub.ar), 7.89 (qAB, 4H, Δvab=122.0 Hz, J=8.4 Hz, H.sub.ar), 7.57-7.54 (m, 2H, H.sub.ar), 7.52 (d, 1H, J=8.9 Hz, H.sub.ar), 7.47 (d, 1H, J=9.9 Hz, CH═), 7.39 (d, 1H, J=2.3 Hz, H.sub.ar), 7.37-7.31 (m, 2H, H.sub.ar), 7.31-7.19 (m, 6H, H.sub.ar), 7.19 (d, 1H, J=8.9 Hz), 7.08 (dd, 4H, J=1.0 Hz, J=8.6 Hz, H.sub.ar), 6.99 (tt, 2H, J=1.0 Hz, J=7.3 Hz, H.sub.ar), 6.45 (d, 1H, J=9.9 Hz, CCH═)

(24) .sup.13C RMN (THF-ds, 400 MHz): δ=152.78, 152.74, 150.15, 149.63, 147.96, 144.43, 143.87, 131.17, 130.69, 130.48, 129.00, 128.88, 127.98, 127.36, 126.64, 126.47, 125.42, 123.74, 122.57, 122.41, 121.86, 120.19, 118.29, 114.49, 81.93.

I.3. Synthesis of (Z)-2-cyano-3-(4-(8-(4-(diphenylamino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)phenyl)acrylic acid (DJ255)

A. 6-(4-(diphenylamino)phenyl)naphthalen-2-ol

(25) ##STR00020##

(26) Under air condition, 2-bromo-6-naphtol (1.00 g, 4.5 mmol) and 4-diphenylamino-phenylboronic acid (1.69 g, 5.8 mmol) and palladium(II) acetate (Pd(OAc).sub.2, 20.1 mg, 89 μmol) were dissolved in isopropanol (iPrOH)/H.sub.2O mixture (150 mL, 2:1). The mixture was heated to reflux and tripotassium phosphate (K.sub.3PO.sub.4, 2.85 g, 13.4 mmol) was added. The mixture was stirred for 2 h before being cooled to room temperature. The organic phase was extracted with EtOAc, dried on sodium sulfate and concentrated. Purification on silica gel using n-hexane/EtOAc (7:3) as eluent to give a white solid (1.30 g, 3.4 mmol, 75%).

(27) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=7.95 (s, 1H, H.sub.ar), 7.79 (d, 1H, J=8.8 Hz, H.sub.ar), 7.74 (d, 1H, J=8.6 Hz, H.sub.ar), 7.69 (dd, 1H, J=1.8 Hz, J=8.6 Hz, H.sub.ar), 7.60 (d, 2H, J=8.6 Hz, H.sub.ar), 7.28 (dd, 4H, J=7.5 Hz, J=8.3 Hz, H.sub.ar), 7.18-7.08 (m, 8H, H.sub.ar) 7.04 (t, 2H, J=7.3 Hz, H.sub.ar), 5.14 (s, 1H, OH).

(28) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=153.56, 147.71, 147.12, 135.70, 134.92, 133.59, 129.98, 129.26, 129.20, 127.68, 126.80, 125.80, 124.78, 124.38, 123.98, 122.94, 118.11, 109.15.

B. 4-(3-(4-bromophenyl)-3-phenyl-3H-benzo[f]chromen-8-yl)-N, N-diphenylaniline

(29) ##STR00021##

(30) Under argon, 1-(4-bromophenyl)-1-phenylprop-2-yn-1-ol (445 mg, 1.55 mmol), 6-(4-(diphenylamino)phenyl)naphthalen-2-ol (400 mg, 1.03 mmol), PPTS (13 mg, 52 μmol) were dissolved in anhydrous 1,2-dichloroethane (5 mL). Trimethyl orthoformate (0.25 mL, 2.1 mmol) was added and the reaction was heated to reflux for 9 h. Solvent was removed under reduced pressure and the crude solid was purified on silica gel using n-hexane/DCM (7:3) as eluent to give a white solid (400 mg, 0.60 mmol, 60%).

(31) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=8.06 (d, 1H, J=8.9 Hz, H.sub.ar), 7.97 (d, 1H, J=1.7 Hz, H.sub.ar), 7.80 (dd, 1H, J=2.0 Hz, J=9.0 Hz), 7.77 (d, 1H, J=9.3 Hz, C═CH), 7.64 (d, 2H, J=8.7 Hz, H.sub.ar), 7.55-7.44 (m, 5H, H.sub.ar), 7.44-7.35 (m, 4H, H.sub.ar), 7.35-7.29 (m, 5H, H.sub.ar), 7.26 (d, 1H, J=8.8 Hz, H.sub.ar), 7.22-7.14 (m, 6H, H.sub.ar), 7.09 (tt, 2H, J=7.3 Hz, J=1.0 Hz, H.sub.ar), 6.33 (d, 1H, J=9.9 Hz, CCH═).

(32) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=150.24, 147.68, 147.24, 144.35, 144.03, 135.88, 134.51, 131.17, 130.18, 129.78, 129.26, 128.76, 128.60, 128.19, 127.71, 127.63, 127.48, 126.78, 125.96, 125.45, 124.41, 123.91, 122.98, 121.91, 121.55, 120.09, 118.50, 114.14.

C. 4-(8-(4-(diphenylamino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)benzaldehyde

(33) ##STR00022##

(34) Under argon, 4-(3-(4-bromophenyl)-3-phenyl-3H-benzo[f]chromen-8-yl)-N,N-diphenylaniline (208 mg, 0.31 mmol) was dissolved in distilled THF. Then n-BuLi (1.1 M, 0.32 mL, 0.34 mmol) was added at −78° C. The reaction was stirred at temperature ranging from −80° C. t −60° C. for 1 h before adding the DMF at −78° C. The reaction was allowed to reach room temperature and stirred for 12 h. The reaction was quenched with water. The organic phase was recovered with EtOAc, dried on sodium sulfate and concentrated under reduced pressure. The crude product is purified on silica gel using DCM/petroleum ether (9:1) as eluent to give a yellow solid (110 mg, 0.18 mmol, 57%).

(35) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=10.01 (s, 1H, CHO), 8.07 (d, 1H, J=8.9 Hz, H.sub.ar), 7.97 (d, 1H, J=1.7 Hz, H.sub.ar), 7.82 (qAB, 4H, J=8.4 Hz, Δv.sub.AB=47.8 Hz, H.sub.ar), 7.80 (dd, 1H, J=2.0 Hz, J=8.7 Hz, H.sub.ar), 7.79 (d, 1H, J=8.5 Hz, H.sub.ar), 7.64 (d, 1H, J=8.7 Hz, H.sub.ar), 7.57-7.53 (m, 2H, H.sub.ar), 7.45 (d, 1H, J=9.9 Hz, CH═), 7.42-7.36 (m, 2H, H.sub.ar), 7.36-727 (m, 6H, H.sub.ar), 7.22-7.14 (m, 6H, H.sub.ar), 7.09 (tt, 2H, J=7.3 Hz, J=1.1 Hz, H.sub.ar), 6.39 (d, 1H, J=9.9 Hz, CCH═).

(36) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=191.63, 151.36, 150.22, 147.68, 147.27, 144.04, 135.97, 135.65, 134.45, 130.30, 129.83, 129.42, 129.28, 128.60, 128.30, 127.90, 127.65, 127.38, 127.14, 126.86, 126.03, 125.46, 124.43, 123.90, 123.00, 121.93, 120.45, 118.48, 114.17, 82.23.

D. (Z)-2-cyano-3-(4-(8-(4-(diphenylamino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)phenyl)acrylic acid (DJ255)

(37) ##STR00023##

(38) 4-(8-(4-(diphenylamino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)benzaldehyde (105 mg, 0.17 mmol), cyanoacetic acid (73 mg, 0.86 mmol), were dissolved in a mixture of acetonitrile (8 mL) and chloroform (5 mL). A catalytic amount of piperidine was added and the solution was refluxed for 3 h. Solvent was removed under reduced pressure and the solid redissolved in chloroform. The organic phase was washed with a HCl solution (2 M), dried on sodium sulfate and concentrated. The crude solid was chromatographed on silica using DCM followed by DCM/MeOH and DCM/MeOH/Acetic acid 96/2/2 as eluents to afford pale yellow solid (45 mg, 0.06 mmol, 40%).

(39) .sup.1H RMN (THF-ds, 400 MHz): δ=8.18 (s, 1H, CH═), 8.03 (d, 1H, J=8.8 Hz, H.sub.ar), 7.95 (d, 1H, J=1.5 Hz, H.sub.ar), 7.93-7.85 (m, 2H, H.sub.ar), 7.75-7.68 (m, 2H, H.sub.ar), 7.63-7.55 (m, 4H, H.sub.ar), 7.49 (d, 2H, J=7.5, H.sub.ar), 7.40 (d, 1H, J=9.9 Hz, CH═), 7.31-7.17 (m, 8H, H.sub.ar), 7.14-7.05 (m, 6H, H.sub.ar), 6.98 (tt, 2H, J=7.3 Hz, J=1.1 Hz, H.sub.ar), 6.34 (d, 1H, J=9.9 Hz, CCH═).

(40) .sup.13C RMN (THF-d.sub.8, 100 MHz): δ=148.46, 147.22, 145.96, 145.34, 142.62, 133.91, 133.01, 129.91, 128.27, 128.20, 128.15, 127.21, 126.94, 126.10, 125.66, 125.52, 125.40, 125.30, 124.86, 123.76, 123.42, 122.30, 122.179, 120.84, 120.04, 118.07, 116.44, 112.24, 80.31.

I.4. Synthesis of (Z)-2-cyano-3-(4′-(8-(diphenylamino)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-yl)acrylic acid (DJ236)

A. 4′-(8-(diphenylamino)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-carbaldehyde

(41) ##STR00024##

(42) Under argon, 3-(4-bromophenyl)-N,N,3-triphenyl-3H-benzo[f]chromen-8-amine (200 mg, 0.34 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzaldehyde (120 mg, 0.52 mmol), Tetrakis(triphenylphosphine)palladium(0) (Pd(PPh.sub.3).sub.4, 8.0 mg, 6.9 μmol) were dissolved in distilled THF. Then an aqueous solution of potassium carbonate (K.sub.2CO.sub.3, 0.5 M, 2.1 mL) was added. The mixture was stirred overnight at reflux.

(43) The reaction was cool to room temperature before extracting the organic phase with diethyl ether. The latter is washed with brine, dried on sodium sulfate and concentrated under reduced pressure. The crude product is purified on silica gel using DCM/petroleum ether (9:1) as eluent to give a white solid (125 mg, 0.20 mmol, 60%).

(44) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=10.07 (s, 1H, CHO), 7.93 (d, 1H, J=9.1 Hz, H.sub.ar), 7.87 (qAB, 4H, Δv.sub.AB=78.3 Hz, J=8.3 Hz, H.sub.ar), 7.67 (qAB, 4H, Δv.sub.AB=11.9 Hz, J=8.7 Hz, H.sub.ar) 7.63-7.59 (m, 2H, H.sub.ar, CH═), 7.50 (d, 1H, J=8.9 Hz), 7.44-7.38 (m, 4H, H.sub.ar), 7.38-7.26 (m, 6H, H.sub.ar), 7.24 (d, 1H, J=8.8 Hz), 7.16-7.11 (m, 4H, H.sub.ar) 7.08 (tt, 2H, J=7.3 Hz, J=1.1 Hz, H.sub.ar), 6.42 (d, 1H, J=9.9 Hz, CCH═)

(45) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=191.69, 149.68, 147.85, 146.36, 145.27, 144.71, 143.89, 138.87, 135.42, 130.47, 130.11, 129.27, 128.93, 128.23, 128.03, 127.69, 127.60, 127.54, 127.12, 126.85, 126.27, 125.59, 124.00, 122.74, 122.55, 121.68, 120.13, 118.60, 114.57, 82.12.

B. (Z)-2-cyano-3-(4′-(8-(diphenylamino)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-yl)acrylic acid (DJ236)

(46) ##STR00025##

(47) 4′-(8-(diphenylamino)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-carbaldehyde (106 mg, 0.17 mmol), cyanoacetic acid (74 mg, 0.87 mmol), were dissolved in a mixture of acetonitrile (8 mL) and chloroform (5 mL). A catalytic amount of piperidine was added and the solution was refluxed for 3 h. Solvent was removed under reduced pressure and the solid redissolved in chloroform. The organic phase was washed with a HCl solution (2 M), dried on sodium sulfate and concentrated. The crude solid was chromatographed on silica using DCM followed by DCM/MeOH and DCM/MeOH/Acetic acid 96/2/2 as eluents to afford pale yellow solid (110 mg, 0.16 mmol, 93%).

(48) .sup.1H RMN (THF-ds, 400 MHz): δ=8.30 (s, 1H, CH═), 8.15 (d, 2H, J=8.4 Hz, H.sub.ar), 7.99 (d, 1H, J=9.1 Hz, H.sub.ar), 7.83 (d, 2H, J=8.4 Hz, H.sub.ar), 7.69 (qAB, 4H, Δv.sub.AB=15.8 Hz, J=8.6 Hz, H.sub.ar), 7.60-7.55 (m, 2H, H.sub.ar), 7.51 (d, 1H, J=8.9 Hz, H.sub.ar), 7.31-7.20 (m, 6H, H.sub.ar), 7.45 (d, 1H, J=9.9 Hz, CH═), 7.39 (d, 1H, J=2.2 Hz, H.sub.ar), 7.37-7.31 (m, 2H, H.sub.ar), 7.18 (d, 1H, J=8.8 Hz, H.sub.ar), 7.11-7.05 (m, 4H, H.sub.ar), 6.99 (tt, 2H, J=7.3 Hz, J=1.1 Hz, H.sub.ar), 6.45 (d, 1H, J=9.9 Hz, CCH═).

(49) .sup.13C RMN (C THF-ds, 100 MHz): δ=162.96, 152.91, 149.82, 147.98, 145.54, 145.02, 144.71, 143.76, 138.45, 131.33, 131.03, 130.62, 128.99, 128.73, 127.98, 127.86, 127.45, 127.27, 127.20, 126.70, 126.59, 126.54, 125.40, 123.71, 122.56, 122.38, 121.94, 119.73, 118.38, 115.42, 114.49, 82.06.

I.5. Synthesis of Z)-2-cyano-3-(4′-(8-(4-(diphenylamino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-yl)acrylic acid (DJ228)

A. 4′-(8-(4-(diphenylamino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-carbaldehyde

(50) ##STR00026##

(51) Under argon, 4-(3-(4-bromophenyl)-3-phenyl-3H-benzo[f]chromen-8-yl)-N,N-diphenylaniline (100 mg, 0.15 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzaldehyde (53 mg, 0.22 mmol), Pd(PPh.sub.3).sub.4 (4.0 mg, 3.1 μmol) were dissolved in distilled THF. Then an aqueous solution of K.sub.2CO.sub.3 (0.5 M, 0.8 mL) was added. The mixture was stirred overnight at reflux. The reaction was cool to room temperature before extracting the organic phase with diethyl ether. The latter was washed with brine, dried on sodium sulfate and concentrated under reduced pressure. The crude product was purified on silica gel using DCM/petroleum ether (7:3) as eluent to give a white solid (78 mg, 0.11 mmol, 75%).

(52) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=10.06 (s, 1H), 8.50 (d, 1H, J=8.3 Hz, CHO), 7.95 (d, 3H, J=8.2 Hz, H.sub.ar), 7.78 (d, 2H, J=8.2 Hz, H.sub.ar), 7.70 (qAB, 4H, J Δvab=20.3 Hz, J=8.6 Hz, H.sub.ar), 7.65 (m, 1H), 7.58 (t, 1H, J=7.2 Hz, H.sub.ar), 7.49 (t, 1H, J=7.1 Hz, H.sub.ar), 7.44-7.38 (m, 2H, H.sub.ar), 7.38-7.30 (m, 6H, H.sub.ar), 7.24-7.16 (m, 6H, H.sub.ar), 7.09 (tt, 2H, J=7.3 Hz, J=0.9 Hz, H.sub.ar), 6.89 (d, 1H, J=9.7 Hz, CH═), 6.38 (d, 1H, J=9.7 Hz, CCH═).

(53) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=191.66, 147.80, 146.88, 146.84, 146.32, 145.48, 144.93, 138.94, 135.41, 134.43, 133.02, 132.70, 130.84, 130.07, 129.26, 128.29, 127.70, 127.61, 127.58, 127.39, 127.20, 126.69, 126.50, 126.07, 125.68, 125.31, 124.80, 124.38, 124.22, 123.40, 122.90, 121.99, 115.39, 82.97.

B. (Z)-2-cyano-3-(4′-(8-(4-(diphenylamino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-yl)acrylic acid (DJ228)

(54) ##STR00027##

(55) 4′-(8-(4-(diphenylamino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-carbaldehyde (30 mg, 44 μmol), cyanoacetic acid (19 mg, 0.22 mmol), were dissolved in a mixture of acetonitrile (8 mL) and chloroform (5 mL). A catalytic amount of piperidine was added and the solution was refluxed for 3 h Solvent was removed under reduced pressure and the solid redissolved in chloroform. The organic phase was washed with a HCl solution (2 M), dried on sodium sulfate and concentrated. The crude solid was chromatographed on silica using DCM followed by DCM/MeOH and DCM/MeOH/Acetic acid 96/2/2 as eluents to afford pale yellow solid (24 mg, 33 μmol, 75%).

(56) .sup.1H RMN (THF-ds, 400 MHz): δ=8.26 (s, ═CH), 8.15-8.07 (m, 3H, H.sub.ar), 7.97 (d, 1H, J=1.6 Hz, H.sub.ar), 7.84-7.71 (m, 5H, H.sub.ar), 7.71-7.60 (m, 6H, H.sub.ar), 7.57-7.52 (m, 2H, H.sub.ar), 7.47 (d, 1H, J=9.9 Hz, CH═), 7.32-7.27 (m, 2H, H.sub.ar), 7.26-7.20 (m, 5H, H.sub.ar), 7.15-7.06 (m, 6H, H.sub.ar), 6.99 (tt, 2H, J=7.3 Hz, J=1.0 Hz, H.sub.ar), 6.42 (d, 1H, J=9.9 Hz, CCH═)

(57) .sup.13C RMN (THF-ds, 100 MHz): δ=150.65, 148.62, 145.97, 145.33, 143.60, 143.15, 142.66, 136.66, 133.87, 133.09, 129.38, 129.30, 128.12, 128.09, 127.20, 126.99, 126.94, 126.01, 125.87, 125.66, 125.60, 125.41, 125.38, 125.27, 125.03, 124.87, 124.74, 123.72, 123.44, 122.28, 122.21, 120.83, 120.01, 117.77, 116.48, 112.26, 80.42.

I.6. Synthesis of (Z)-2-cyano-3-(4′-(6-(4-(diphenylamino)phenyl)-2-phenyl-2H-benzo[h]chromen-2-yl)-[1,1′-biphenyl]-4-yl)acrylic acid (DJ277)

A. 4-(4-methoxynaphthalen-1-yl)-N,N-diphenylaniline

(58) ##STR00028##

(59) Under air condition, 1-methoxy-6-bromonaphtalene (0.79 g, 3.3 mmol) and 4-diphenylamino-phenylboronic acid (1.6 g, 4.33 mmol) and PdOAc (15.0 mg, 67 μmol) were dissolved in iPrOH/H.sub.2O mixture (150 mL, 2:1). The mixture was heated to reflux and K.sub.3PO.sub.4 (2.12 g, 10.0 mmol) was added. The mixture was stirred for 2 h at 80° C. before being cooled to room temperature. The organic phase was extracted with EtOAc, dried on sodium sulfate and concentrated. The crude product was purified on silica gel using n-hexane/EtOAc (95:5) as eluent to give a white solid (1.30 g, 3.2 mmol, 97%).

(60) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=8.35 (dd, 1H, J=2.1 Hz, J=7.3 Hz, H.sub.ar), 8.00 (dd, 1H, J=2.0 Hz, J=7.4 Hz, H.sub.ar), 7.54-7.50 (m, 2H, H.sub.ar), 7.42-7.37 (m, 3H, H.sub.ar), 7.36-7.30 (m, 4H, H.sub.ar), 7.23-7.17 (m, 5H, H.sub.ar), 7.14 (dd, 1H, J=2.8 Hz, J=8.1 Hz, H.sub.ar), 7.09 (td, 2H, J=7.9 Hz, J=1.0 Hz, H.sub.ar), 6.94 (d, 2H, J=7.9 Hz, H.sub.ar), 4.08 (s, 3H, CH.sub.3).

(61) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=154.79, 147.87, 146.71, 135.01, 132.45, 130.94, 129.26, 127.19, 126.83, 126.37, 125.70, 125.03, 124.30, 124.01, 123.58, 122.83, 122.07, 103.55, 55.55.

B. 4-(4-(diphenylamino)phenyl)naphthalen-1-ol

(62) ##STR00029##

(63) Under argon, 4-(4-methoxynaphthalen-1-yl)-N,N-diphenylaniline (0.50 g, 1.2 mmol) was dissolved in DCM and boron tribromide (BBr.sub.3, 0.16 mL, 1.6 mmol) was added at 0° C. The reaction was stirred at room temperature for 3 h before being quenched with a K.sub.2CO.sub.3 saturated solution. The organic phase was extracted with DCM, dried on sodium sulfate and concentrated. The crude product was purified on silica gel using n-hexane/EtOAc (8:2) as eluent to give a white solid (0.38 g, 1.0 mmol, 80%).

(64) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ==8.28 (dd, 1H, J=2.1 Hz, J=7.3 Hz, H.sub.ar), 8.02 (dd, 1H, J=2.0 Hz, J=7.4 Hz, H.sub.ar), 7.58-7.49 (m, 2H, H.sub.ar), 7.41-7.30 (m, 7H, H.sub.ar), 7.24-7.17 (m, 6H, H.sub.ar), 7.09 (tt, 2H, J=7.3 Hz, J=1.0 Hz, H.sub.ar), 6.94 (d, 2H, J=7.7 Hz, H.sub.ar), 5.49 (s, 1H, OH).

(65) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=150.81, 147.85, 146.75, 134.89, 132.74, 132.69, 130.92, 129.25, 126.76, 126.42, 125.91, 125.07, 124.47, 124.31, 123.54, 122.84, 121.75, 108.18.

C. 4-(2-(4-bromophenyl)-2-phenyl-2H-benzo[h]chromen-6-yl)-N,N-diphenylaniline

(66) ##STR00030##

(67) Under argon, 1-(4-bromophenyl)-1-phenylprop-2-yn-1-ol (411 mg, 1.43 mmol), 4-(4-(diphenylamino)phenyl)naphthalen-1-ol (370 mg, 0.95 mmol), PPTS (12 mg, 52 μmol) were dissolved in anhydrous 1,2-dichloroethane (6 mL). Trimethyl orthoformate (0.21 mL, 1.91 mmol) was added and the reaction was heated to reflux for 9 h. Solvent was removed under reduced pressure and the crude solid was purified on silica gel using n-hexane/DCM (6:4) as eluent to give a white solid (250 mg, 0.38 mmol, 40%).

(68) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=8.45 (d, 1H, J=8.0 Hz, H.sub.ar), 7.96 (d, 1H, J=8.4 Hz, H.sub.ar), 7.62-7.44 (m, 9H H.sub.ar), 7.41-7.30 (m, 9H, H.sub.ar), 7.24-7.16 (m, 9H, H.sub.ar), 7.09 (tt, 2H, J=7.3 Hz, J=0.9 Hz, H.sub.ar), 6.86 (d, 1H, J=9.7 Hz, CH═), 6.28 (d, 1H, J=9.7 Hz, CCH═).

(69) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=147.82, 146.90, 144.62, 134.43, 133.09, 132.71, 131.29, 130.87, 129.28, 128.68, 128.37, 128.31, 127.91, 127.77, 127.34, 126.68, 126.53, 126.08, 125.71, 125.29, 124.77, 124.40, 124.34, 123.43, 122.93, 121.93, 121.62, 115.34, 82.80.

D. 4′-(6-(4-(diphenylamino)phenyl)-2-phenyl-2H-benzo[h]chromen-2-yl)-[1,1′-biphenyl]-4-carbaldehyde

(70) ##STR00031##

(71) Under argon, 4-(2-(4-bromophenyl)-2-phenyl-2H-benzo[h]chromen-6-yl)-N,N-diphenylaniline (180 mg, 0.27 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzaldehyde (70 mg, 0.30 mmol), Pd(PPh.sub.3).sub.4 (9.5 mg, 8.2 μmol) were dissolved in distilled THF. Then an aqueous solution of K.sub.2CO.sub.3 (0.5 M, 1.6 mL) was added. The mixture was stirred overnight at reflux. The reaction was cool to room temperature before extracting the organic phase with diethyl ether. The latter was washed with brine, dried on sodium sulfate and concentrated under reduced pressure. The crude product was purified on silica gel using DCM/petroleum ether (7:3) as eluent to give a white solid (150 mg, 0.22 mmol, 80%).

(72) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=10.06 (s, 1H), 8.50 (d, 1H, J=8.3 Hz, CHO), 7.95 (d, 3H, J=8.2 Hz, H.sub.ar), 7.78 (d, 2H, J=8.2 Hz, H.sub.ar), 7.70 (qAB, 4H, J Δvab=20.3 Hz, J=8.6 Hz, H.sub.ar), 7.65 (m, 1H), 7.58 (t, 1H, J=7.2 Hz, H.sub.ar), 7.49 (t, 1H, J=7.1 Hz, H.sub.ar), 7.44-7.38 (m, 2H, H.sub.ar), 7.38-7.30 (m, 6H, H.sub.ar), 7.24-7.16 (m, 6H, H.sub.ar), 7.09 (tt, 2H, J=7.3 Hz, J=0.9 Hz, H.sub.ar), 6.89 (d, 1H, J=9.7 Hz, CH═), 6.38 (d, 1H, J=9.7 Hz, CCH═).

(73) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=191.66, 147.80, 146.88, 146.84, 146.32, 145.48, 144.93, 138.94, 135.41, 134.43, 133.02, 132.70, 130.84, 130.07, 129.26, 128.29, 127.70, 127.61, 127.58, 127.39, 127.20, 126.69, 126.50, 126.07, 125.68, 125.31, 124.80, 124.38, 124.22, 123.40, 122.90, 121.99, 115.39, 82.97.

E. (Z)-2-cyano-3-(4′-(6-(4-(diphenylamino)phenyl)-2-phenyl-2H-benzo[h]chromen-2-yl)-[1,1′-biphenyl]-4-yl)acrylic acid (DJ277)

(74) ##STR00032##

(75) 4′-(6-(4-(diphenylamino)phenyl)-2-phenyl-2H-benzo[h]chromen-2-yl)-[1,1′-biphenyl]-4-carbaldehyde (230 mg, 0.34 mmol), cyanoacetic acid (143 mg, 1.69 mmol), were dissolved in a mixture of acetonitrile (8 mL) and chloroform (12 mL). A catalytic amount of piperidine was added and the solution was refluxed for 3 h. Solvent was removed under reduced pressure and the solid redissolved in chloroform. The organic phase was washed with a HCl solution (2 M), dried on sodium sulfate and concentrated. The crude solid was chromatographed on silica using DCM followed by DCM/MeOH and DCM/MeOH/Acetic acid 96/2/2 as eluents to afford pink solid (204 mg, 0.26 mmol, 80%).

(76) .sup.1H RMN (THF-ds, 400 MHz): δ=8.50 (d, 1H, J=8.3 Hz, H.sub.ar), 8.30 (s, 1H, CH═), 8.15 (d, 2H, J=8.4 Hz, H.sub.ar), 7.91 (d, 1H, J=8.3 Hz, H.sub.ar), 7.83 (d, 2H, J=8.4 Hz, H.sub.ar), 7.73 (s, 4H, H.sub.ar), 7.66-7.62 (m, 1H, H.sub.ar), 7.53 (ddd, 1H, J=1.2 Hz, J=6.8 Hz, J=8.2 Hz, H.sub.ar), 7.44 (ddd, 1H, J=1.2 Hz, J=6.8 Hz, J=8.2 Hz, H.sub.ar), 7.38-7.33 (m, 4H, H.sub.ar), 7.32-7.26 (m, 5H, H.sub.ar), 7.22 (s, 1H, H.sub.ar), 7.19-7.14 (m, 6H, H.sub.ar), 7.04 (tt, 2H, J=1.2 Hz, J=7.3 Hz, H.sub.ar), 6.88 (d, 1H, J=9.8 Hz, CCH═) ppm 6.42 (d, 1H, J=9.7 Hz, CH═).

(77) .sup.13C RMN (THF-ds, 100 MHz): δ=162.92, 152.93, 147.91, 146.93, 146.90, 145.72, 145.23, 144.66, 138.56, 134.73, 132.83, 132.74, 131.34, 131.04, 130.71, 129.11, 128.00, 127.58, 127.39, 127.32, 127.27, 126.73, 126.64, 126.16, 125.82, 125.32, 124.88, 124.27, 123.71, 123.28, 122.73, 121.94, 115.40, 115.25, 83.14.

I.7. Synthesis of (E)-2-cyano-3-(4′-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)-[1,1′-biphenyl]-4-yl)acrylic acid (YKC5P21)

A. Methyl-5-bromo-2-(4-methoxynaphthalen-1-yl) benzoate

(78) ##STR00033##

(79) Under argon, after 1-bromo-4-methoxynaphthalene (400 mg, 1.69 mmol) was dissolved in distilled THF (20 mL), n-BuLi (675 μL, 1.69 mmol, 1 eq) was added dropwise at −78° C. The solution was stirred for 30 min before adding a solution of zinc bromide (418 mg, 1.86 mmol, 1.1 eq) in 5 mL of THF. The solution was kept stirred at −78° C. during 1 h. In a separate flask, methyl 5-bromo-2-iodobenzoate (600 mg, 1.76 mmol) and palladium tetrakis (101.7 mg, 5% mol) were previously dried before including the zinc product solution. The reaction was stirred in the cold bath for 2 h and left stirred overnight at room temperature. The reaction was quenched with HCl solution (1 M). The organic phase was extracted with diethyl ether and washed with water and brine, dried over sodium sulphate, filtered and concentrated under vacuum. The crude product was purified by chromatography on silica gel using n-hexane/DCM: 9/1, then 8/2 and 6/4 as eluent to afford white solid (531 mg, 1.43 mmol, 81.3%).

(80) .sup.1H NMR (CDCl.sub.3, 200 MHz): δ=8.30 (d, 1H, J=8.3 Hz, H.sub.ar), 8.10 (d, 1H, J=2.0 Hz, H.sub.ar), 7.68 (dd, 1H, J=2.1 Hz, J=8.2 Hz, H.sub.ar), 7.44 (m, 1H, H.sub.ar), 7.37 (m, 2H, H.sub.ar), 7.26 (s, 1H, H.sub.ar), 7.00 (ABq, 2H, Δvab=140.0 Hz, J=7.85 Hz, H.sub.ar), 4.02 (s, 3H, OCH.sub.3), 3.39 (s, 3H, OCH.sub.3).

(81) .sup.13C NMR (CDCl.sub.3, 50 MHz): δ=166.7, 155.2, 140.3, 134.4, 133, 9, 133.5, 132.8, 132.7, 130.5, 126.7, 126.0, 125.3, 125.1, 125.0, 122.3, 121.1, 103.7, 55.5, 52.1, 31.6, 22.7, 14.1.

B. 9-bromo-7,7-bis(4-hexylphenyl)-5-methoxy-7H-benzo[c]fluorene

(82) ##STR00034##

(83) Previously under argon, (4-hexylphenyl)magnesium bromide was prepared from 1(4-bromophenyl)hexane (1.0 g, 4.15 mmol) and magnesium (100 mg, 4.15 mmol, 1 eq) in 5 mL freshly distillated THF. This reaction mixture was stirred at reflux for 1 h. In a second flask, methyl 5-bromo-2-(4-methoxynaphthalen-1-yl) benzoate (500 mg, 1.35 mmol) was solubilized in 15 mL THF. Then the Grignard reagent was added dropwise and the solution was heated to reflux overnight. After cooling to room temperature, the crude mixture was poured into water. The organic layer was extracted twice with ethyl acetate and washed by water and brine, dried over sodium sulphate, filtered and concentrated under vacuum overnight. The crude was dissolved in glacial acetic acid (40 mL). After 30 min, 4 mL concentrated HCl were added dropwise and refluxed at 120° C. for 5 h. After back to room temperature, the acetic acid was removed by rotary evaporation, and the crude was extracted by pentane. The organic layer was washed several times by water and dried over sodium sulphate, filtered and concentrated under vacuum. The crude product was purified by chromatography on silica gel using n-hexane/DCM: 98/5 as eluent to afford colorless oil (273 mg, 0.42 mmol, 39.1%).

(84) .sup.1H NMR (CDCl.sub.3, 200 MHz): δ=8.69 (d, 1H, J=8.4 Hz, H.sub.ar), 8.43 (dd, 1H, J=0.9 Hz, J=0.9 Hz, 8.4H.sub.ar), 8.17 (d, 1H, J=8.3 Hz, H.sub.ar), 7.72 (m, 1H, H.sub.ar), 7.37 (m, 2H, H.sub.ar), 7.63 (m, 1H, H.sub.ar), 7.58 (m, 2H, H.sub.ar), 7.18 (ABq, 8H, Δvab=32.1 Hz, J=8.3 Hz, H.sub.ar), 6.93 (s, 1H, H.sub.ar), 3.99 (s, 3H, OCH.sub.3), 2.53 (t, 4H, CH.sub.2), 1.55 (m, 4H, CH.sub.2), 1.28 (m, 12H, CH.sub.2), 0.87 (t, 6H, CH.sub.3).

(85) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ=156.1, 154.8, 151.3, 141.9, 141.6, 140.5, 130.4, 130.0, 128.9, 128.3, 128.1, 127.5, 125.9, 125.7, 125.0, 123.5, 123.3, 123.1, 119.2, 102.1, 65.3, 55.7, 35.5, 31.7, 31.6, 31.3, 29.1, 22.6, 14.0.

C. 7,7-bis(4-hexylphenyl)-5-methoxy-N,N-diphenyl-7H-benzo[c]fluoren-9-amine

(86) ##STR00035##

(87) Under argon, Pd.sub.2dba.sub.3 (3.54 mg, 3.87 μmol) and tri-tert-butylphosphine tetrafluoroborate (2.25 mg, 7.74 μmol) were dissolved with anhydrous toluene (5 mL). After stirred for 15 min, a solution of 9-bromo-7,7-bis(4-hexylphenyl)-5-methoxy-7H-benzo[c]fluorene (268 mg, 415 μmol) and diphenylamine (77.26 mg, 456.5 μmol) in anhydrous toluene (20 mL) was added. Potassium tert-butoxide (143.4 mg, 1.28 mmol, 3.3 eq) was added and the resulting mixture was stirred for 30 min at room temperature before being refluxed for 48 h. The melt was filtered through celite and poured into HCl (1 M). The organic phase was extracted with diethyl ether, washed with water, dried over Na.sub.2SO.sub.4 and concentrated. The crude oil was purified by chromatography on silica using n-hexane/DCM: 8/2 as eluent to afford pale yellow oil (299 mg, 407 μmol, 98.1%).

(88) .sup.1H NMR (CDCl.sub.3, 200 MHz): δ=8.60 (d, 1H, J=8.4 Hz, H.sub.ar), 8.31 (dd, 1H, J=0.9 Hz, J=0.9 Hz, H.sub.ar), 8.05 (d, 1H, J=8.5 Hz, H.sub.ar), 7.59 (m, 1H, H.sub.ar), 7.47 (m, 1H, H.sub.ar), 7.27 (d, 1H, J=2.2 Hz, H.sub.ar), 7.17 (m, 4H, H.sub.ar), 7.10-6.93 (m, 15H, H.sub.ar), 6.83 (s, 1H, H.sub.ar), 3.88 (s, 3H, OCH.sub.3), 2.53 (t, 4H, CH.sub.2), 1.55 (m, 4H, CH.sub.2), 1.28 (m, 12H, CH.sub.2), 0.87 (t, 6H, CH.sub.3).

(89) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ=155.23, 154.16, 150.56, 147.76, 145.45, 142.64, 141.24, 136.28, 129.92, 129.13, 128.31, 128.18, 127.20, 127.09, 125.72, 124.83, 124.03, 123.81, 123.19, 122.99, 122.56, 122.44, 121.80, 102.60, 65.25, 55.69, 35.59, 31.791 31.43, 29.17, 22.67, 14.15.

D. 9-(diphenylamino)-7,7-bis(4-hexylphenyl)-7H-benzo[c]fluoren-5-ol

(90) ##STR00036##

(91) Under argon, a solution of 7,7-bis(4-hexylphenyl)-5-methoxy-N,N-diphenyl-7H-benzo[c]fluoren-9-amine (290 mg, 0.40 mmol) in 7 mL of DCM was put at 0° C. Tribromoborane (48.74 μL, 0.5 mmol, 1.3 eq) was added dropwise. The solution was allowed to reach room temperature and stirred for 3 h. Then the reaction was quenched with a saturated solution of K.sub.2CO.sub.3. The organic phase was extracted with DCM, dried over Na.sub.2SO.sub.4 and concentrated. The crude was purified by chromatography on silica using n-hexane/ethyl acetate: 8/2 as eluent to afford white solid (250 mg, 347 μmol, 87.9%).

(92) .sup.1H NMR (acetone-d.sub.6, 400 MHz): δ=9.21 (s, 1H, OH), 8.77 (m, 1H, H.sub.ar), 8.41 (m, 1H, H.sub.ar), 8.05 (d, 1H, J=8.5 Hz, H.sub.ar), 8.26 (m, 1H, H.sub.ar), 7.69 (m, 1H, H.sub.ar), 7.56 (m, 1H, H.sub.ar), 7.38-6.93 (m, 20H, H.sub.ar), 2.59 (t, 4H, CH.sub.2), 1.60 (m, 4H, CH.sub.2), 1.33 (m, 12H, CH.sub.2), 0.89 (t, 6H, CH.sub.3).

(93) .sup.13C NMR (acetone-d.sub.6, 100 MHz): δ=143.07, 131.53, 131.13, 130.01, 129.77, 127.62, 126.70, 125.80, 124.62, 121.93, 119.37, 37.04, 33.42, 33.25, 24.24, 15.33.

E. 1-(4-bromophenyl)-1-phenylprop-2-yn-1-ol

(94) ##STR00037##

(95) Under argon, sodium acetylide (3.68 g, 76.6 mmol, 18 wt % in xylene) was dissolved in anhydrous THF. 4-bromobenzophenone (2.00 g, 7.6 mmol) was added in one portion at 0° C. After reaching room temperature the reaction mixture was stirred for 3 h. Then a NH.sub.4Cl saturated solution was added to the reaction and stirred for 10 min. The organic phase was extracted with Et.sub.2O, dried on sodium sulfate and concentrated. The crude was purified on silica gel using DCM as eluent to give a pale yellow solid (1.75 g, 6.1 mmol, 80%).

(96) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=7.63-7.58 (m, 2H, H.sub.ar), 7.49 (qAB, 4H, J Δvab=9.1 Hz, J=8.6 Hz, H.sub.ar), 7.40-7.27 (m, 3H, H.sub.ar), 3.11 (s, 1H, OH), 2.97 (s, 1H, C≡CH).

(97) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=144.19, 143.87, 131.35, 128.41, 128.06, 127.80, 125.82, 121.81, 85.78, 75.87, 73.81.

F. 3-(4-bromophenyl)-13,13-bis(4-hexylphenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-11-amine

(98) ##STR00038##

(99) Under argon, 1-(4-bromophenyl)-1-phenylprop-2-yn-1-ol (150 mg, 0.52 mmol), 9-(diphenylamino)-7,7-bis(4-hexylphenyl)-7H-benzo[c]fluoren-5-ol (250 mg, 0.35 mmol), PPTS (4.4 mg, 17 μmol) were dissolved in anhydrous 1,2-dichloroethane (6 mL). Trimethyl orthoformate (75 μL, 0.70 mmol) was added and the reaction was heated to reflux for 9 h. Solvent was removed under reduced pressure and the crude solid was purified on silica gel using n-hexane/DCM (9:1) as eluent to give a pale green solid (197 mg, 0.20 mmol, 57.5%).

(100) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=8.60 (d, 1H, J=8.4 Hz, H.sub.ar), 8.42 (dd, 1H, J=1.0 Hz, J=0.9 Hz, 8.4H.sub.ar), 8.02 (d, 1H, J=8.5 Hz, H.sub.ar), 7.60 (m, 1H, H.sub.ar), 7.53 (m, 1H, H.sub.ar), 7.35-7.32 (m, 4H, H.sub.ar), 7.27-7.17 (m, 10H, H.sub.ar), 7.11-7.07 (m, 4H, H.sub.ar), 7.03-6.95 (m, 11H, H.sub.ar), 6.72 (d, 1H, J=9.81 Hz, H.sub.ar), 5.81 (d, 1H, J=9.81 Hz, H.sub.ar), 2.58 (m, 4H, CH.sub.2), 1.60 (m, 4H, CH.sub.2), 1.31 (m, 12H, CH.sub.2), 0.87 (t, 6H, CH.sub.3).

(101) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=156.7, 147.5, 146.2, 146.0, 143.8, 143.4, 141.6, 141.5, 139.5, 139.4, 135.1, 131.0, 129.1, 128.9, 128.8, 128.7, 128.1, 128.0, 127.9, 127.6, 127.5, 127.3, 126.8, 126.7, 125.4, 125.3, 124.1, 123.9, 123.2, 122.8, 122.7, 122.4, 122.2, 122.2, 121.5, 121.4, 120.4, 115.1, 35.4, 31.7, 31.5, 31.4, 29.1, 22.6, 13.8.

G. 4′-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)-[1,1′-biphenyl]-4-carbaldehyde

(102) ##STR00039##

(103) Under argon, chromene 3-(4-bromophenyl)-13,13-bis(4-hexylphenyl)-N,N,3-triphenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-11-amine (195 mg, 0.20 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzaldehyde (60 mg, 0.27 mmol), Pd(PPh.sub.3).sub.4 (4.5 mg, 3.9 μmol) were dissolved in distilled THF. Then an aqueous solution of K.sub.2CO.sub.3 (0.5 M, 1.6 mL) was added. The mixture was stirred overnight at reflux. The reaction was cool to room temperature before extracting the organic phase with diethyl ether. The latter is washed with brine, dried on sodium sulfate and concentrated under reduced pressure. The crude product is purified on silica gel using petroleum ether/Et.sub.2O (7:3) as eluent to give a pale green solid (120 mg, 0.12 mmol, 60%).

(104) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=10.01 (s, 1H, CHO), 8.60 (d, 1H, J=8.4 Hz, H.sub.ar), 8.48 (dd, 1H, J=1.0 Hz, J=0.9 Hz, 8.4H.sub.ar), 8.02 (d, 1H, J=8.5 Hz, H.sub.ar), 7.80 (ABq, 4H, Δvab=89.2 Hz, J=7.80 Hz, H.sub.ar), 7.60-7.39 (m, 7H, H.sub.ar), 7.29-6.90 (m, 24H, H.sub.ar), 6.74 (d, 1H, J=9.81 Hz, H.sub.ar), 5.90 (d, 1H, J=9.81 Hz, H.sub.ar), 2.59 (m, 4H, CH.sub.2), 1.59 (m, 4H, CH.sub.2), 1.30 (m, 12H, CH.sub.2), 0.85 (t, 6H, CH.sub.3).

(105) .sup.13C RMN (CD.sub.2Cl.sub.2, 100 MHz): δ=191.64, 146.37, 141.55, 141.47, 139.59, 139.46, 138.78, 135.38, 130.03, 129.60, 129.09, 128.97, 128.85, 128.78, 128.11, 128.03, 127.97, 127.58, 127.54, 127.265, 126.98, 126.79, 125.33, 124.18, 124.14, 124.08, 123.96, 123.13, 122.81, 122.74, 120.46, 81.97, 64.598, 35.45, 31.73, 31.47, 29.10, 22.60, 13.84.

H. (E)-2-cyano-3-(4′-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)-[1,1′-biphenyl]-4-yl)acrylic acid (YKC5P21)

(106) ##STR00040##

(107) 4′-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)-[1,1′-biphenyl]-4-carbaldehyde (100 mg, 0.10 mmol), cyanoacetic acid (83 mg, 0.98 mmol), were dissolved in a mixture of acetonitrile (8 mL) and chloroform (12 mL). A catalytic amount of piperidine was added and the solution was refluxed for 3 h. Solvent was removed under reduced pressure and the solid redissolved in chloroform. The organic phase was washed with an HCl solution (2 M), dried on sodium sulfate and concentrated. The crude solid was chromatographed on silica using DCM followed by DCM/MeOH and DCM/MeOH/Acetic acid 96/2/2 as eluents to afford pale green solid (94 mg, 0.09 mmol, 88%).

(108) .sup.1H RMN (THF-ds, 400 MHz): δ=8.69 (d, 1H, J=8.4 Hz, H.sub.ar), 8.52 (dd, 1H, J=1.0 Hz, J=0.9 Hz, 8.4H.sub.ar), 8.28 (s, 1H, H.sub.ar), 8.15-8.11 (m, 3H, H.sub.ar), 7.80 (d, 2H, J=8.5 Hz, H.sub.ar), 7.64-7.61 (m, 3H, H.sub.ar), 7.56-7.42 (m, 6H, H.sub.ar), 7.28-7.15 (m, 11H, H.sub.ar), 7.08-6.95 (m, 11H, H.sub.ar), 6.80 (d, 1H, J=9.81 Hz, H.sub.ar), 5.95 (d, 1H, J=9.81 Hz, H.sub.ar), 2.59 (m, 4H, CH.sub.2), 1.66 (m, 4H, CH.sub.2), 1.35 (m, 12H, CH.sub.2), 0.91 (t, 6H, CH.sub.3).

(109) .sup.13C RMN (THF-ds, 100 MHz): δ=158.13, 149.02, 147.72, 147.18, 145.64, 142.42, 141.23, 141.18, 139.86, 136.77, 132.66, 131.11, 129.21, 129.17, 129.01, 128.63, 128.38, 128.23, 127.92, 126.89, 126.39, 125.31, 124.30, 123.86, 123.74, 123.66, 122.01, 116.51, 36.82, 33.14, 32.98, 30.55, 28.18, 23.93, 14.84.

I.8. Synthesis of (Z)-3-(4′-(8-(4-(bis(4-hexylphenyl)amino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-yl)-2-cyanoacrylic acid (DJ307)

A. 4-hexyl-N-(4-hexylphenyl)-N-(4-(6-methoxynaphthalen-2-yl)phenyl)aniline

(110) ##STR00041##

(111) 4-(N,N-di((4-hexyloxy)phenyl)amine)phenyl-(4,4,5,5-tetra methyl-1,3,2-dioxa)-borolane was already described by Yum et al, 2009 [10].

(112) Under air condition, 2-bromo-6-methoxynaphtalene (235 mg) and 4-(N,N-di((4-hexyloxy)phenyl)amine)phenyl-(4,4,5,5-tetramethyl-1,3,2-dioxa)-borolane (616 mg) and PdOAc (4.5 mg) were dissolved in iPrOH/H.sub.2O mixture (50 mL, 2:1). The mixture was heated to reflux and K.sub.3PO.sub.4 (632 mg) was added. The mixture was stirred for 2 h at 80° C. before being cooled to room temperature. The organic phase was extracted with diethylether, washed with brine, dried on sodium sulfate and concentrated. Purification on silica gel using n-hexane/dichloromethane (6/4 in volume) as eluent to give a white solid (440 mg, 77%).

(113) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): 0.90 (t, 6H, —CH3, J=7.33 Hz); 1.33 (m, 12H); 1.62 (m, 4H); 2.58 (t, 4H); 3.92 (m, 3H, —OCH3); 7.01-7.18 (m, 12H); 7.57 (m, 2H); 7.72 (m, 1H); 7.76 (m, 2H); 7.94 (m, 1H)

B. 6-(4-(bis(4-hexylphenyl)amino)phenyl)naphthalen-2-ol

(114) ##STR00042##

(115) Under argon, the methoxy-protected precursor (470 mg, 1 eq) was dissolved in distilled THF (10 mL). Then BBr.sub.3 (270 mg, 1.3 eq) was added at 0° C. The reaction was allowed to reach room temperature in 3 h under vigorous stirring. Then the reaction was quenched with K.sub.2CO.sub.3, saturation solution. The organic phase was extracted with DCM and dried with sodium sulfate. After concentration under vacuum the purification was carried out on silica gel using a mixture of n-hexane and EtOAc as eluent (8/2 in volume). A second purification with DCM as eluent was necessary to recover the pure product (370 mg, 83%).

(116) .sup.1H RMN (CD.sub.2Cl.sub.2, 200 MHz): δ=8.03 (s, 1H, H.sub.ar), 7.87 (d, 1H, J=8.8 Hz, H.sub.ar), 7.79 (m, 2H, H.sub.ar), 7.65 (d, 2H, J=8.8 Hz, H.sub.ar), 7.15-7.30 (m, 12H, H.sub.ar), 5.58 (s, 1H, OH), 2.69 (t, 4H, J=7.6 Hz, H.sub.alk), 1.73 (q, 4H, J=7.6 Hz, H.sub.alk), 1.50-1.40 (m, 10H), 1.03 (t, 6H).

C. 4-(3-(4-bromophenyl)-3-phenyl-3H-benzo[f]chromen-8-yl)-N, N-bis(4-hexylphenyl)aniline

(117) ##STR00043##

(118) Under argon, 1-(4-bromophenyl)-1-phenylprop-2-yn-1-ol (246 mg), 6-(4-(bis(4-hexylphenyl)amino)phenyl)naphthalen-2-ol (318 mg), PPTS (7.1 mg) were dissolved in anhydrous 1,2-dichloroethane (6 mL). Trimethyl orthoformate (0.13 mL) was added and the reaction was heated to reflux overnight. Solvent was removed under reduced pressure and the crude solid was purified on silica gel using n-hexane/DCM (7:3 in volume) as eluent to give a white solid (360 mg, 63%).

(119) RMN .sup.1H (CD.sub.2Cl.sub.2): 1.10 (t, 6H, —CH.sub.3); 1.53 (m, 12H); 1.80 (m, 4H); 2.78 (m, 4H); 6.50 (d, 1H, J=9.90 Hz); 7.20-7.33 (m, 9H); 7.41 (d, 2H, J=8.83 Hz); 7.56 (m, 3H); 7.65-7.72 (m, 7H); 7.76 (d, 2H, J=8.66 Hz); 7.91-7.98 (m, 2H); 8.12 (m, 1H); 8.22 (d, 1H, J=8.84 Hz)

D. 4′-(8-(4-(bis(4-hexylphenyl)amino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-carbaldehyde

(120) ##STR00044##

(121) Under argon, 4-(3-(4-bromophenyl)-3-phenyl-3H-benzo[f]chromen-8-yl)-N,N-bis(4-hexylphenyl)aniline (110 mg), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzaldehyde (46 mg), Pd(PPh.sub.3).sub.4 (5 mg) were dissolved in distilled THF. Then an aqueous solution of K.sub.2CO.sub.3 (0.5 M, 0.8 mL) was added. The mixture was stirred 48 h at reflux. The reaction was cool to room temperature before extracting the organic phase with dichloromethane. The latter was washed with brine, dried on sodium sulfate and concentrated under reduced pressure. The crude product was purified on silica gel using DCM/hexanes ether (1/1) as eluent to give a white solid (80 mg, 70%).

(122) .sup.1H RMN (CD.sub.2Cl.sub.2, 400 MHz): δ=10.15, (s, 1H, Aldehyde), 8.2 (d, 1H, J=8.9 Hz, H.sub.ar), 8.1 (d, 1H, J=1.6 Hz, H.sub.ar), 8.02 (d, 2H, J=8.45 Hz), 7.93 (dd, 2H, J=1.84 Hz, J=8.3 Hz), 7.90 (d, 2H, J=8.4 Hz), 7.74 (d, 2H, J=8.7 Hz, H.sub.ar), 7.69 (d, 2H, J=8.8 Hz, H.sub.ar), 7.60 (d, 2H, J=9.9 Hz, C═CH), 7.52 (t, 2H, J=7.8 Hz, H.sub.ar), 7.47 (d, 1H, J=7.2 Hz), 7.42 (d, 1H, J=7.2 Hz) 7.28 (t, 5H, J=8.3 Hz, H.sub.ar), 7.21 (d, 3H, J=8.4 Hz, H.sub.ar), 6.53 (d, 1H, J=9.9 Hz, C═CH), 2.76 (t, 4H, J=7.8 Hz), 1.8 (q, 4H, J=7.6 Hz), 1.46-1.59 (m, 12H), 1.05-1.12 (m, 6H).

E. (Z)-3-(4′-(8-(4-(bis(4-hexylphenyl)amino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-yl)-2-cyanoacrylic acid (DJ307)

(123) ##STR00045##

(124) 4′-(8-(4-(bis(4-hexylphenyl)amino)phenyl)-3-phenyl-3H-benzo[f]chromen-3-yl)-[1,1′-biphenyl]-4-carbaldehyde (70 mg), cyanoacetic acid (35 mg), were dissolved in a mixture of acetonitrile (10 mL) and chloroform (5 mL). A catalytic amount of piperidine was added and the solution was refluxed for 3 h. Solvent was removed under reduced pressure and the solid redissolved in chloroform. The organic phase was washed with HCl solution (2 M), dried on sodium sulfate and concentrated. The crude solid was chromatographed on silica using DCM followed by DCM/MeOH and DCM/MeOH/Acetic acid 96/2/2 as eluents to afford pale yellow solid (25 mg, 33%).

(125) RMN .sup.1H (THF D.sup.8, 400 MHz): δ=0.90 (t, 6H, —CH.sub.3); 1.33 (m, 12H); 1.60 (m, 4H); 2.56 (m, 4H); 6.41 (d, 1H, J=9.94 Hz); 7.00 (m, 4H); 7.07 (m, 5H); 7.22 (m, 2H); 7.30 (m, 2H); 7.47 (d, 1H, J=9.92 Hz); 7.56 (m, 4H); 7.65 (m, 4H); 7.72-7.76 (m, 2H); 7.79 (m, 3H); 7.94 (m, 1H); 8.07-8.12 (m, 3H); 8.26 (s, 1H)

(126) .sup.13C RMN: (THF D.sup.8, 100 MHz): δ=163.68 (C═O), 153.73, 151.18, 148.38, 146.35, 146.31, 145.80, 145.50, 139.25, 138.19, 136.66, 134.81, 132.12 (2C), 131.80, 130.78, 130.70, 129.74 (4C), 129.55, 128.65 (2C), 128.49, 128.25 (2C), 128.10, 128.06 (2C), 128.01, 127.51 (2C), 127.39, 126.36, 125.91, 125.77, 125.08 (4C), 123.82, 123.07, 122.60, 121.74, 120.45, 119.08, 116.18, 114.90, 104.29, 83.04 (C-spiro), 36.03 (2C), 32.53 (2C), 32.42 (2C), 29.84 (2C), 23.32 (2C), 14.23 (2C).

I.9. Synthesis of (E)-2-cyano-3-(5-(4-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)phenyl)thiophen-2-yl)acrylic acid (LG36)

A. 5-(4-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)phenyl)thiophene-2-carbaldehyde

(127) ##STR00046##

(128) Under argon, chromene 3-(4-bromophenyl)-13,13-bis(4-hexylphenyl)-N,N,3-triphenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-11-amine (245 mg, 0.25 mmol), the (5-formylthiophen-2-yl)boronic acid (43 mg, 0.73 mmol) and the Pd(PPh3)4 (9 mg, 7.4 μmol) were dissolved degassed and dry toluene (3 mL) and distilled THF (24 mL). After the total dissolution of the reactants the base, K.sub.2CO.sub.3 (0.5M, 1.5 mL) is added and the solution was heated over 70° C. overnight. The mixture is directly concentrated them quenched with HCl 1M, exacted with diethyl ether and washed with water and saturated sodium chloride solution. The crude mixture is purified on silica by column chromatography using hexane/Et2O: 9/1 as eluent and then purified on silica gel column chromatography hexane/DCM: 5/5. Finally it was purified on silica gel by column chromatography with hexane/THF: 95/5 as eluent to give a green solid (28%).

(129) .sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz): δ=9.59 (s, 1H, CHO), 8.61 (d, J=8.0 Hz, 1H, H.sub.ar), 8.47 (dd, J=1.2 Hz, J=8.4 Hz, 1H, H.sub.ar), 8.03 (d, J=8.4 Hz, 1H, H.sub.ar), 7.68 (dt, J=2 Hz, J=8.8 Hz, 2H, H.sub.ar), 7.63-7.52 (m, 3H, H.sub.ar), 7.45 (dt, J=2 Hz, J=8.8 Hz, 2H, H.sub.ar), 7.37-7.35 (m, 2H, H.sub.ar), 7.28 (d, J=3.6 Hz, 1H, H.sub.ar), 7.24-7.16 (m, 7H, H.sub.ar), 7.11-7.09 (m, 4H, H.sub.ar), 7.04-6.98 (m, 9H, Har), 6.95 (s, 2H, H.sub.ar), 6.81 (d, J=3.6 Hz, 1H, H.sub.ar), 6.75 (d, J=10 Hz, 1H, H.sub.alkene), 5.88 (d, J=10 Hz, 1H, H.sub.alkene), 2.60 (m, 4H, CH.sub.2), 1.61 (m, 4H, CH.sub.2), 1.32 (m, 12H, CH2), 0.89 (m, 6H, CH.sub.3).

(130) .sup.13C NMR (CD.sub.2Cl.sub.2, 400 MHz): δ=177.60, 159.32, 157.26, 152.80, 148.09, 146.90, 146.51, 144.34, 142.12, 140.12, 140.05, 136.39, 135.67, 131.27, 130.18, 129.38, 128.97, 128.87, 128.80, 128.61, 128.25, 128.10, 127.87, 127.70, 127.44, 125.99, 125.94, 125.65, 125.49, 124.70, 124.55, 123.86, 123.54, 123.34, 123.01, 122.86, 120.99, 115.79, 108.50, 82.55, 65.18, 36.05, 32.34, 32.10, 29.71, 23.22, 14.46

B. (E)-2-cyano-3-(5-(4-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)phenyl)thiophen-2-yl)acrylic acid (LG36)

(131) ##STR00047##

(132) 5-(4-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)phenyl)thiophene-2-carbaldehyde (70 mg, 69 μmol), and the 2-cianoacetic acid (58 mg, 0.69 mmol) are dried under vacuum before their dissolution in distilled acetonitrile (5 mL) and anhydrous chloroform (4 mL). Two drop of piperidine were added before heating at 70° C. during 4 hours. The mixture was directly concentrated then neutralized with HCl 1M, extracted with DCM and washed with water. The solution is dried under sodium sulfate, concentrated under vacuum and the crude mixture was purified by column chromatography with three different eluents, the first was 100% DCM, the second was DCM with 2% methanol and the third was DCM with 2% methanol and 2% acetic acid. A green solid is obtained (69 mg, 94%).

(133) .sup.1H NMR (THF, 400 MHz): δ=8.66 (d, J=8.4 Hz, 1H, H.sub.ar), 8.49 (d, J=8 Hz, 1H, H.sub.ar), 8.09 (d, J=8.4 Hz, 1H, H.sub.ar), 7.96 (s, 1H, COOH), 7.81 (d, J=8.4 Hz, 2H, H.sub.ar), 7.69 (q, J=3.2 Hz, 1H, H.sub.ar), 7.59-7.47 (m, 5H, H.sub.ar), 7.40 (d, J=7.6 Hz, 2H, H.sub.ar), 7.32 (d, J=3.6 Hz, 1H, H.sub.ar), 7.24-7.10 (m, 12H, H.sub.ar), 7.06-6.92 (m, 11H, H.sub.ar), 6.77 (d, J=9.6 Hz, 1H, H.sub.alkene), 5.92 (d, J=9.6 Hz, 1H, H.sub.alkene), 2.62 (m, 4H, CH2), 1.62 (m, 4H, CH2), 1.37 (m, 12H, CH2), 0.95 (m, 6H, CH3).

(134) .sup.13C NMR (THF, 400 MHz): δ=169.05, 167.47, 159.56, 157.57, 149.15, 148.38, 147.10, 146.54, 144.84, 142.04, 141.79, 140.58, 140.42, 137.89, 136.11, 133.44, 131.37, 130.46, 129.66, 129.62, 129.39, 129.14, 128.97, 128.64, 128.55, 128.41, 128.05, 127.90, 127.74, 127.54, 126.28, 125.83, 125.49, 124.69, 123.85, 123.64, 123.25, 123.14, 123.01, 121.37, 116.07, 109.69, 82.79, 64.72, 36.21, 32.54, 32.38, 29.94, 23.33, 14.26.

I.10. Synthesis of (Z)-2-cyano-3-(4-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)phenyl)acrylic acid [YKC5P98]

A. (4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)(phenyl)methanone [YKC5P60]

(135) ##STR00048##

(136) Under argon, N,O-dimethylhydroxylamine hydrochloride (729 mg, 1.5 eq), was dissolved in anhydrous DCM (110 mL). The solution was cooled to 0° C. and stirred 5 min before the addition of trimethylamine (1.26 g, 2.5 eq). After, benzoyl chloride (700 mg, 5 mmol) was added dropwise and stirred for 30 min at 0° C. and the cold bath was left for stirred overnight at room temperature. The mixture was treated with a NaHCO.sub.3 saturated solution and the organic phase was extracted with DCM, dried on sodium sulfate and concentrated. A flash purification was performed on silica gel using Hexane/Et.sub.2O: 8/2 as eluent to afford a pale oil of N-methoxy-N-methylbenzamide which used after.

(137) In a second flask, under argon 2-(4-bromophenyl)-5,5-dimethyl-1,3-dioxane (1 g, 3.7 mmol) is dissolved in distilled THF (15 mL), n-BuLi (1.62 mL, 4 mmol, 1.1 eq) is added dropwise at −78° C. The solution was stirred for 1 h before addition of a solution of N-methoxy-N-methylbenzamide (610 mg, 1 eq) in 10 mL of THF. The reaction was stirred for 20 h and at room temperature. The reaction was quenched with water and the organic phase was extracted with diethyl ether and washed with brine, dried over sodium sulphate, filtered and concentrated under vacuum. The crude was purified by chromatography on silica gel using n-hexane/Et.sub.2O: 5/5 as eluent to afford white solid (800 mg, 2.7 mmol, 73.2%).

(138) .sup.1H NMR (CDCl.sub.3, 400 MHz): δ=7.8 (m, 4H, H.sub.ar), 7.63 (m, 2H, H.sub.ar), 7.58 (m, 1H, H.sub.ar), 7.47 (m, 2H, H.sub.ar), 5.47 (s, 1H, CH), 3.81 (d, 2H, J=11.2 Hz, CH.sub.2), 3.68 (d, 2H, J=11.2 Hz, CH.sub.2), 1.31 (s, 3H, CH.sub.3), 0.82 (s, 3H, CH.sub.3).

(139) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ=196.46, 142.47, 137.95, 137.57, 132.45, 130.08, 128.25, 126.13, 100.95, 77.70, 30.29, 23.03, 21.86.

B. 1-(4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)-1-phenylprop-2-yn-1-ol [YKC5P63]

(140) ##STR00049##

(141) Under argon, sodium acetylide (7.2 g, 27 mmol, 18 wt % in xylene) was dissolved in anhydrous THF (200 mL). (4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)(phenyl)methanone (800 mg, 2.7 mmol) was added in one portion at 0° C. After reaching room temperature the reaction mixture was stirred for 3 h. Then a NH.sub.4Cl saturated solution was added to the reaction and stirred for 30 min. The organic phase was extracted with Et.sub.2O, dried on sodium sulfate and concentrated. The crude was purified on silica gel using n-hexane/THF: 85/15 as eluent to give a white solid (811 mg, 2.5 mmol, 93.2%).

(142) .sup.1H NMR (CDCl.sub.3, 400 MHz): δ=7.61 (m, 2H, H.sub.ar), 7.56 (m, 2H, H.sub.ar), 7.48 (m, 2H, H.sub.ar), 7.30 (m, 2H, H.sub.ar), 7.27 (m, 1H, H.sub.ar), 5.38 (s, 1H, CH), 3.76 (d, 2H, J=11.2 Hz, CH.sub.2), 3.64 (d, 2H, J=11.2 Hz, CH.sub.2), 2.86 (s, 1H, C≡CH), 2.77 (s, 1H, OH), 1.27 (s, 3H, CH.sub.3), 0.79 (s, 3H, CH.sub.3).

(143) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ=144.95, 138.10, 128.25, 127.86, 126.12, 125.99, 101.34, 77.64, 75.57, 30.22, 23.01, 21.87.

C. 4-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)benzaldehyde

(144) ##STR00050##

(145) Under argon, propargylic alcohol [YKC5P63] (269 mg, 0.84 mmol, 1.5 eq), naphtol [YKC5P16] (400 mg, 0.35 mmol), Pyridinium p-toluenesulfonate [PPTS] (7 mg, 27.8 μmol) was dissolved in anhydrous 1,2-dichloroethane (10 mL). Trimethyl orthoformate (121 μL, 1.10 mmol) was added and the reaction was heated at 65° C. overnight. Solvent was removed under reduced pressure and the crude solid was purified on silica gel using n-hexane/acetone: 95/5 as eluent to give a green oil (197 mg, 0.20 mmol). In a flask, this oil was put with p-toluenesulfonic acid (70 mg, 1.3 eq) in a mix of 10 mL of THF and 4 mL of HCl conc. This mixture was refluxed for 3 h and was treated with a NaHCO.sub.3 saturated. The organic phase was extracted with Et.sub.2O, dried on sodium sulfate and concentrated. Purification was performed on silica gel using n-hexane/acetone: 95/5 as eluent to give a green solid (181 mg, 0.19 mmol, 31.8%).

(146) .sup.1H RMN (CDCl.sub.3, 400 MHz): δ=9.91 (s, 1H, CHO), 8.57 (d, 1H, J=8.3 Hz, H.sub.ar), 8.45 (dd, 1H, J=1.1 Hz, J=8.3 Hz, H.sub.ar), 7.98 (d, 1H, J=8.6 Hz, H.sub.ar), 7.61 (ABq, 4H, Δvab=74.9 Hz, J=8.40 Hz, H.sub.ar), 7.59-7.54 (m, 2H, H.sub.ar), 7.33-7.30 (m, 2H, H.sub.ar), 7.25-7.10 (m, 13H, H.sub.ar), 7.01-6.91 (m, 12H, H.sub.ar), 6.76 (d, 1H, J=9.81 Hz, H.sub.ar), 5.80 (d, 1H, J=9.81 Hz, H.sub.ar), 2.58 (m, 4H, CH.sub.2), 1.61 (m, 4H, CH.sub.2), 1.31 (m, 12H, CH.sub.2), 0.87 (t, 6H, CH.sub.3).

(147) .sup.13C RMN (CDCl.sub.3, 100 MHz): δ=191.77, 156.59, 151.07, 147.48, 147.36, 146.27, 145.76, 143.38, 141.23, 141.21, 139.60, 139.51, 135.37, 135.17, 129.68, 129.44, 129.03, 128.90, 128.57, 128.17, 127.95, 127.92, 127.75, 127.58, 127.19, 126.88, 126.23, 125.28, 124.03, 123.71, 122.94, 122.59, 122.41, 122.34, 120.67, 115.14, 81.89, 64.56, 35.53, 31.73, 31.46, 31.42, 29.11, 22.61, 14.09.

D. (Z)-2-cyano-3-(4-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)phenyl)acrylic acid [YKC5P98]

(148) ##STR00051##

(149) 4-(11-(diphenylamino)-13,13-bis(4-hexylphenyl)-3-phenyl-3,13-dihydrobenzo[h]indeno[2,1-f]chromen-3-yl)benzaldehyde [YKC5P96] (175 mg, 0.19 mmol), cyanoacetic acid (158 mg, 1.87 mmol, 10 eq), were dissolved in a mixture of acetoneitrile (15 mL) and chloroform (15 mL). A catalytic amount of piperidine was added and the solution was refluxed for 12 h. Solvent was removed under reduced pressure and the solid was dissolved in chloroform. The organic phase was washed with an HCl solution (2M), dried on sodium sulfate and concentrated. The crude solid was chromatographed on silica using DCM followed by DCM/MeOH: 98/2 and DCM/MeOH/Acetic acid: 96/2/2 as eluents to afford blue-green solid (151 mg, 0.15 mmol, 80.5%).

(150) .sup.1H RMN (THF-d8, 400 MHz): δ=8.65 (d, 1H, J=8.4 Hz, H.sub.ar), 8.48 (dd, 1H, J=1.0 Hz, J=0.9 Hz, 8.4H.sub.ar), 8.16 (s, 1H, H.sub.ar), 8.08 (d, 1H, J=8.6 Hz, H.sub.ar), 7.91 (d, 2H, J=8.5 Hz, H.sub.ar), 7.58 (m, 1H, H.sub.ar), 7.52-7.5 (m, 3H, H.sub.ar), 7.39 (m, 2H, H.sub.ar), 7.24-7.10 (m, 12H, H.sub.ar), 7.06-6.92 (m, 11H, H.sub.ar), 6.79 (d, 1H, J=9.81 Hz, H.sub.ar), 5.91 (d, 1H, J=9.81 Hz, H.sub.ar), 2.60 (m, 4H, CH.sub.2), 1.63 (m, 4H, CH.sub.2), 1.33 (m, 12H, CH.sub.2), 0.89 (t, 6H, CH.sub.3).

(151) .sup.13C RMN (THF-d8, 100 MHz): δ=156.81, 152.57, 149.18, 147.60, 147.45, 146.29, 145.86, 143.72, 141.27, 141.08, 139.74, 135.25, 131.30, 130.41, 129.72, 128.91, 128.52, 127.98, 127.86, 127.82, 127.61, 127.44, 127.11, 126.70, 126.52, 125.45, 125.16, 123.96, 123.41, 122.83, 122.53, 122.420 122.21, 120.52, 115.23, 81.88, 64.62, 35.43, 35.37, 31.76, 31.62, 29.15, 22.56, 13.50.

II. Tests in Solar Cells

(152) The devices were prepared as followed: the layer of TiO.sub.2 films were screen-printed (ordered from Solaronix). The electrode total active area was 0.36 cm.sup.2. A layer of transparent titania was deposited with a TiO.sub.2 nanoparticles paste (Ti-Nanoxide HT/SP) obtained from Solaronix, Switzerland. In order to optimize adhesion, titania layer porosity and specific area a pre and post TiCl.sub.4 treatment was performed.

(153) After sintering at 500° C. and cooling down to 70° C., the sintered TiO.sub.2 electrodes were sensitized by immersion in a solution of the dye in indicated solvent with or without chenodeoxycholic acid (CDCA) for at least 1 h but preferentially 3 h or longer in SPrAM, and then assembled using a thermally platinized FTO/glass (TCO 22-7, Solaronix) counter electrode. The working and counter electrodes were separated by a 60 μm thick hot melt gasket (Meltonix 1170-25, Solaronix) and sealed by heating. The heating was minimized to avoid dye thermal degradation.

(154) The cell was then filled with a volatile electrolyte (Solaronix Iodolyte HI-30) through a pre-drilled hole using a vacuum pump. The electrolyte injection hole on the thermally platinized FTO glass counter electrode was finally sealed with a thin glass cover.

(155) Devices using a non-volatile ionic liquid based electrolyte (Solaronix Mosalyte TDE-250) were prepared following the previously described procedure with a 25 μm thick hot melt gasket. The devices were characterized using a Oriel SP94023 A (Xe lamp) solar simulator (AAA) previously calibrated. The current-voltage characteristics of the cell measured under AM 1.5G, 100% sun, were obtained by applying external potential bias to the cell and by measuring the generated photocurrent with a Keithley model 2400 digital source meter (Keithley, USA). The devices were masked prior to measurement according to a procedure previously described to attain an illuminated active area of 0.36 cm.sup.2.

III. Results Obtained with the Organic Dyes According to the Invention

III.1. Absorption Spectrum of the Organic Dyes According to the Invention

(156) The organic dye DJ277 shows a reversible photochromic behavior and can absorb UV light up to 400 nm in the close form (FF) giving rise to the formation of the colored species (FO) that can absorb photons up to 500-550 nm (FIG. 1).

(157) The organic dye YKC5P21 presents a range of absorption of the close form (FF) in the UV shifted up to 450 nm (FIG. 1). This gives rise to a better light absorption even in devices and as a consequence the absorption range of the colored species (FO). The chemical modification of YKC5P21 compared to DJ277 i.e. a more extended pi-conjugated system with a fused ring makes it possible to improve the coloration upon irradiation even in devices.

III.2. Power Conversion Efficiencies

(158) Results obtained in a device configuration with organic chromophoric dyes according to the present invention (DJ255, DJ277 and YKC5P21) are presented respectively in Tables 1, 2 and 3 hereafter.

(159) The devices were irradiated using a solar simulator with a power of irradiation of 1000 W/m.sup.2 at 25° C. The I(V) curves were recorded at different interval time and the photovoltaic parameters were measured.

(160) The power conversion efficiency is calculated by η=P_max/P_in 100%, where P_max is the maximum generated power and P_in the electrical input power from the light source. The important parameter connected with the efficiency is the field factor, which is the ratio of the maximum power to the theoretical power FF=P_max/P_theor=P_max/(V_oc J_sc), with Voc the open circuit voltage (for I=0) and Jsc the short circuit current (for V=0). So the efficiency can be written q=(J_sc V_(oc) FF)/P_in 100%

(161) The results below indicate that upon irradiation the dyes switch from the uncolored form to the colored form. With increasing the time of irradiation the amount of colored dye increases and the photosensitization of the TiO.sub.2 electrode occurs. For this reason the solar cell becomes more and more colored and the current density increases (FIG. 2). After few minutes an equilibrium is reached.

(162) Conditions with DJ255

(163) Dyeing bath: [dye]=0.5 mM. [CDCA]=5.0 mM in Ethanol:CHCl.sub.3 1:1

(164) Electrolyte: [I.sub.2]=9 mM. [LiI]=0.5 M. [.sup.tBP]=0.5 M. [GThio]=0.1 M in ACN

(165) Thickness: 8 μm. No scattering layer

(166) TABLE-US-00001 TABLE 1 (DJ255) V.sub.OC (V) J.sub.SC (mA/cm.sup.2) FF PCE (%) t0 0.467 2.46 64 0.73 t0 + 13 s 0.468 2.51 64 0.75 t0 + 26 s 0.467 2.59 64 0.77 t0 + 39 s 0.464 2.64 64 0.78 t0 + 52 s 0.462 2.65 62 0.76 t0 + 65 s 0.460 2.69 63 0.78 t0 + 77 s 0.458 2.70 64 0.79 t0 + 90 s 0.456 2.71 64 0.79 t0 + 102 s 0.454 2.72 64 0.79 t0 + 114 s 0.453 2.74 64 0.79 t0 + 128 s 0.452 2.75 64 0.79
Conditions with DJ277

(167) Dyeing bath: [dye]=0.5 mM. [CDCA]=5.0 mM in Ethanol:CHCl.sub.3 1:1

(168) Electrolyte: [I.sub.2]=9 mM. [LiI]=0.5 M. [.sup.tBP]=0.5 M. [GThio]=0.1 M in ACN

(169) Thickness: 8 μm. No scattering layer

(170) TABLE-US-00002 TABLE 2 (DJ277) V.sub.OC (V) J.sub.SC (mA/cm.sup.2) FF (%) PCE (%) t0 0.47 4.17 63 1.22 t0 + 71 s 0.46 4.77 62 1.39 t0 + 131 s 0.46 4.91 62 1.38 t0 + 175 s 0.46 4.97 61 1.37

(171) Conditions with YKC5P21 (Test 1)

(172) Dyeing bath: [dye]=0.5 mM. [CDCA]=5.0 mM in Ethanol:CHCl.sub.3 1:1

(173) Electrolyte: [I.sub.2]=9 mM. [LiI]=0.5 M. [.sup.tBP]=0.5 M. [GThio]=0.1 M in ACN

(174) Thickness: 12 μm. No scattering layer

(175) TABLE-US-00003 TABLE 3 (YKC5P21-test 1) V.sub.OC (V) J.sub.SC (mA/cm.sup.2) FF PCE (%) t0 0.42 6.92 1.77 t0 + 20 s 0.42 7.94 2.13 t0 + 35 s 0.42 8.44 2.26 t0 + 53 s 0.42 8.72 2.31 t0 + 70 s 0.41 8.97 2.34 t0 + 83 s 0.41 9.08 2.34

(176) Conditions with YKC5P21 (Test 2)

(177) Dyeing bath: [dye]=0.5 mM. [CDCA]=20.0 mM in Ethanol:CHCl.sub.3 1:1

(178) Electrolyte: [I.sub.2]=9 mM. [LiI]=0.5 M. [.sup.tBP]=0.5 M. [GThio]=0.1 M in ACN

(179) Thickness: 12 μm. No scattering layer

(180) TABLE-US-00004 TABLE 4 (YKC5P21-test 2) V.sub.OC (V) J.sub.SC (mA/cm.sup.2) FF PCE (%) t0 0.458 1.42 0.67 0.44 t0 + 15 s 0.463 1.67 0.68 0.53 t0 + 57 s 0.502 8.02 0.59 2.38 t0 + 74 s 0.494 8.83 0.60 2.61 t0 + 92 s 0.488 9.24 0.59 2.68 t0 + 108 s 0.484 9.46 0.59 2.71 t0 + 126 s 0.481 9.59 0.59 2.73 t0 + 144 s 0.476 9.71 0.59 2.75 t0 + 159 s 0.473 9.78 0.59 2.76 t0 + 83 s 0.41 9.08 0.59 2.34

(181) The last test was carried out to demonstrate that the solar cells show a reversible photochromic behaviour.

(182) Note that in this case the solar cells were fabricated with a scattering layer, this explains the rapid coloration and the rapid increase of efficiency.

(183) After irradiation the solar cells were stored for 16 h in the dark and tested again in the same conditions. The solar cells were decoloured, indicating that the photochromic behaviour is reversible.

(184) Conditions with YKC5P21 (Test 3)

(185) Dyeing bath: [dye]=0.5 mM. [CDCA]=20.0 mM in Ethanol:CHCl.sub.3 1:1

(186) Electrolyte: [I.sub.2]=9 mM. [LiI]=0.5 M. [.sup.tBP]=0.5 M. [GThio]=0.1 M in CAN

(187) Thickness: 12 μm.+ scattering layer 4 μm

(188) TABLE-US-00005 TABLE 4 (YKC5P21-test 3) DAY 1 V.sub.OC (V) J.sub.SC (mA/cm.sup.2) FF PCE (%) t0 0.49 8.36 0.61 2.55 t0 + 18 s 0.49 8.94 0.62 2.74 t0 + 57 s 0.48 9.06 0.62 2.73 DAY 2 The solar cell was decoloured after 16 h in the dark t0 + 0 s 0.44 7.98 0.62 2.25 t0 + 14 s 0.45 8.77 0.65 2.57 t0 + 29 s 0.44 9.11 0.65 2.67 t0 + 45 s 0.44 9.37 0.65 2.72 t0 + 60 s 0.44 9.54 0.65 2.76 t0 + 89 s 0.44 9.63 0.64 2.78

(189) Conditions with YKC5P98

(190) Dyeing bath: [dye]=0.5 mM. [CDCA]=5.0 mM in Tertiobutanol:CHCl.sub.3 1:1

(191) Electrolyte: [I.sub.2]=10 mM. [LiI]=0.5 M. [.sup.tBP]=0.5 M. [GThio]=0.1 M in ACN

(192) Thickness: 8 μm+4 μm scattering layer

(193) TABLE-US-00006 TABLE 5 (YKC5P98) V.sub.OC (V) J.sub.SC (mA/cm.sup.2) FF (%) PCE (%) t0 + 40 s 0.50 3.10 71 1.12

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