Photosensitizer and photoelectric conversion element

Abstract

The invention provides a photosensitizer which has excellent conversion efficiency and durability. A photosensitizer which is characterized by being a dye represented by formula (I) or a salt thereof. In the chemical formula, m represents an integer of 0-4; n represents an integer of 0 or 1; p represents an integer of 0-2; each of R1, R2 and R3 represents a hydrogen atom, an alkyl group, an aryl group or the like; each of R4, R4', R4", R5, R6, R7, R8 and R9 represents a hydrogen atom, an alkyl group or the like; X represents a carbonyl group or the like; and each of Z1 and Z2 represents a carboxyl group or the like.

Description

technical field

[0001] The present invention relates to a photosensitizer and a photoelectric conversion element using the photosensitizer. Background technique

[0002] Among organic solar cells attracting attention as next-generation solar cells in recent years, there are broadly divided into organic thin-film type and dye-sensitized type. Organic thin-film solar cells combine organic materials to make p-n junctions and utilize them. The working mechanism is exactly the same as that of inorganic solar cells represented by silicon. In contrast, dye-sensitized solar cells (Dye Sensitized Solar Cells, DSCs) are characterized by the use of modified electrodes that combine organic dyes as photosensitizers with inorganic semiconductors such as titanium oxide and zinc oxide. , In addition, the working mechanism of dye-sensitized solar cells is completely different from that of inorganic solar cells, rather close to photosynthesis. This solar cell, which should be called an inor...

Examples

Embodiment 1

[0163]

[0164] Aldehyde (B-01) (0.88 g) and intermediate (C-01) (0.50 g) were dissolved in acetic acid (10 mL), and heated and stirred at 100° C. for 4 hours. The reaction mixture was cooled to room temperature and solidified. The crude crystals were separated by filtration, and were separated by column chromatography (silica gel, developer: CHCl 3 / MeOH=100 / 1) was separated and purified, whereby 0.85 g of a pigment (I-03) was obtained as a brown solid (69% yield). λmax=545nm (CHCl 3 ).

[0165] The structure of the obtained pigment (I-03) was identified by NMR analysis.

[0166] 1 H NMR (400MHz, DMSO-d 6 )

[0167] δ (ppm) = 13.65 (1H, br.s), 8.67 (1H, br.s), 8.33 (1H, dd, J = 8.0, 7.6Hz), 8.24 (1H, d, J = 11.6Hz), 8.20 (1H,br.s),7.94(1H,dd,J=7.6,7.6Hz),7.65(1H,s),7.41-7.49(3H,m),7.30-7.38(5H,m),7.19-7.23 (4H,m),7.11(1H,s),7.07(2H,d,J=8.4Hz),6.87(1H,d,J=8.8Hz),5.07-5.11(1H,m),3.82-3.87( 1H,m),2.03-2.12(1H,m),1.69-1.83(2H,m),1.59-1.67(2H,m),1.27-1.38(1H,m)

Embodiment 2

[0168]

[0169] Using the same method as in Example 1, and using an aldehyde intermediate (B-02), a pigment (I-05) was obtained as a black solid. λmax=541nm (CHCl 3 ).

[0170] The structure of the obtained pigment (I-05) was identified by NMR analysis.

[0171] 1 H NMR (400MHz, DMSO-d 6 )

[0172] δ(ppm)=13.63(1H,br.s),8.72(1H,br.s),8.35(1H,d,J=8.0Hz),8.28(1H,br.s),8.25(1H,d, J=11.6Hz),7.95(1H,dd,J=8.0,7.6Hz),7.90(1H,d,J=8.4Hz),7.83(1H,d,J=7.2Hz),7.69(1H,s) ,7.67(1H,d,J=1.6Hz),7.56(1H,d,J=7.2Hz),7.41(1H,dd,J=8.0,1.2Hz),7.36(1H,dd,J=8.0,7.2 Hz), 7.32(1H,dd,J=8.4,7.2Hz),6.87(1H,d,J=8.4Hz),5.24-5.27(1H,m),3.90-3.94(1H,m),2.08-2.18 (1H,m),1.74-1.88(3H,m),1.64-1.73(1H,m),1.50(3H,s),1.47(3H,s),1.37-1.53(1H,m)

Embodiment 3

[0173]

[0174] Using the same method as in Example 1, and using an aldehyde intermediate (B-03), a pigment (I-06) was obtained as a black solid. λmax=546nm (CHCl 3 ).

[0175] The structure of the obtained pigment (I-06) was identified by NMR analysis.

[0176] 1 H NMR (400MHz, DMSO-d 6 )

[0177] δ (ppm) = 13.07 (1H, br.s), 8.17 (1H, br.s), 7.81 (1H, dd, J = 7.6, 7.2Hz), 7.73 (2H, d, J = 9.6Hz), 7.41 (1H,d,J=8.0Hz),7.34(1H,d,J=8.4Hz),7.27(1H,d,J=7.2Hz),7.14(1H,s),6.99(1H,s),6.92 (1H,d,J=6.8Hz),6.88(1H,d,J=8.0Hz),6.83(1H,dd,J=7.2,6.0Hz),6.80(1H,dd,J=7.2,6.4Hz) ,6.30(1H,d,J=8.4Hz),4.72-4.75(1H,m),3.36-3.40(1H,m),1.57-1.65(1H,m),1.43-1.56(4H,m),1.28 -1.35(1H,m),1.11-1.26(3H,m),0.84-0.95(1H,m),0.45-0.59(4H,m),0.16(3H,t,J=7.2Hz),0.10(3H ,t,J=7.2Hz),0.02-0.04(4H,m)

technical field

[0001] The present invention relates to a photosensitizer and a photoelectric conversion element using the photosensitizer. Background technique

[0002] Among organic solar cells attracting attention as next-generation solar cells in recent years, there are broadly divided into organic thin-film type and dye-sensitized type. Organic thin-film solar cells combine organic materials to make p-n junctions and utilize them. The working mechanism is exactly the same as that of inorganic solar cells represented by silicon. In contrast, dye-sensitized solar cells (Dye Sensitized Solar Cells, DSCs) are characterized by the use of modified electrodes that combine organic dyes as photosensitizers with inorganic semiconductors such as titanium oxide and zinc oxide. , In addition, the working mechanism of dye-sensitized solar cells is completely different from that of inorganic solar cells, rather close to photosynthesis. This solar cell, which should be called an inor...

Examples

Embodiment 1

[0163]

[0164] Aldehyde (B-01) (0.88 g) and intermediate (C-01) (0.50 g) were dissolved in acetic acid (10 mL), and heated and stirred at 100° C. for 4 hours. The reaction mixture was cooled to room temperature and solidified. The crude crystals were separated by filtration, and were separated by column chromatography (silica gel, developer: CHCl 3 / MeOH=100 / 1) was separated and purified, whereby 0.85 g of a pigment (I-03) was obtained as a brown solid (69% yield). λmax=545nm (CHCl 3 ).

[0165] The structure of the obtained pigment (I-03) was identified by NMR analysis.

[0166] 1 H NMR (400MHz, DMSO-d 6 )

[0167] δ (ppm) = 13.65 (1H, br.s), 8.67 (1H, br.s), 8.33 (1H, dd, J = 8.0, 7.6Hz), 8.24 (1H, d, J = 11.6Hz), 8.20 (1H,br.s),7.94(1H,dd,J=7.6,7.6Hz),7.65(1H,s),7.41-7.49(3H,m),7.30-7.38(5H,m),7.19-7.23 (4H,m),7.11(1H,s),7.07(2H,d,J=8.4Hz),6.87(1H,d,J=8.8Hz),5.07-5.11(1H,m),3.82-3.87( 1H,m),2.03-2.12(1H,m),1.69-1.83(2H,m),1.59-1.67(2H,m),1.27-1.38(1H,m)

Embodiment 2

[0168]

[0169] Using the same method as in Example 1, and using an aldehyde intermediate (B-02), a pigment (I-05) was obtained as a black solid. λmax=541nm (CHCl 3 ).

[0170] The structure of the obtained pigment (I-05) was identified by NMR analysis.

[0171] 1 H NMR (400MHz, DMSO-d 6 )

[0172] δ(ppm)=13.63(1H,br.s),8.72(1H,br.s),8.35(1H,d,J=8.0Hz),8.28(1H,br.s),8.25(1H,d, J=11.6Hz),7.95(1H,dd,J=8.0,7.6Hz),7.90(1H,d,J=8.4Hz),7.83(1H,d,J=7.2Hz),7.69(1H,s) ,7.67(1H,d,J=1.6Hz),7.56(1H,d,J=7.2Hz),7.41(1H,dd,J=8.0,1.2Hz),7.36(1H,dd,J=8.0,7.2 Hz), 7.32(1H,dd,J=8.4,7.2Hz),6.87(1H,d,J=8.4Hz),5.24-5.27(1H,m),3.90-3.94(1H,m),2.08-2.18 (1H,m),1.74-1.88(3H,m),1.64-1.73(1H,m),1.50(3H,s),1.47(3H,s),1.37-1.53(1H,m)

Embodiment 3

[0173]

[0174] Using the same method as in Example 1, and using an aldehyde intermediate (B-03), a pigment (I-06) was obtained as a black solid. λmax=546nm (CHCl 3 ).

[0175] The structure of the obtained pigment (I-06) was identified by NMR analysis.

[0176] 1 H NMR (400MHz, DMSO-d 6 )

[0177] δ (ppm) = 13.07 (1H, br.s), 8.17 (1H, br.s), 7.81 (1H, dd, J = 7.6, 7.2Hz), 7.73 (2H, d, J = 9.6Hz), 7.41 (1H,d,J=8.0Hz),7.34(1H,d,J=8.4Hz),7.27(1H,d,J=7.2Hz),7.14(1H,s),6.99(1H,s),6.92 (1H,d,J=6.8Hz),6.88(1H,d,J=8.0Hz),6.83(1H,dd,J=7.2,6.0Hz),6.80(1H,dd,J=7.2,6.4Hz) ,6.30(1H,d,J=8.4Hz),4.72-4.75(1H,m),3.36-3.40(1H,m),1.57-1.65(1H,m),1.43-1.56(4H,m),1.28 -1.35(1H,m),1.11-1.26(3H,m),0.84-0.95(1H,m),0.45-0.59(4H,m),0.16(3H,t,J=7.2Hz),0.10(3H ,t,J=7.2Hz),0.02-0.04(4H,m)

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