# Patent

## Title
Bacteriochlorin-based organic dye

## Abstract

Disclosed herein is a bacteriochlorin-based organic dye represented by Formula (II):




wherein the substituents contained in Formula (II) are as defined herein. The bacteriochlorin-based organic dye is stable in air, and may be used as a photosensitizer in dye-sensitized solar cell.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority of Taiwanese Application No. 105111516, filed on Apr. 13, 2016.
FIELD
The disclosure relates to an organic dye, and more particularly to a bacteriochlorin-based organic dye.
BACKGROUND
In the development of solar cell applications, dye-sensitized solar cells (DSSCs) have a high potential. A photosensitizer contained in DSSCs absorbs visible light and ultraviolet light in sunlight, and electrons contained in the photosensitizer are thus excited and effectively introduced to a conduction band of a semiconductor electrode so as to produce a photocurrent. Therefore, the quality of the photosensitizer may affect the photoelectric conversion efficiency of DSSCs. The photosensitizer commonly used in DSSC includes ruthenium complexes, porphyrin derivatives, and small molecular organic photosensitizers having electron-donating and electron-withdrawing structures.
US 2003/0203888 A1 discloses a bacteriochlorin chromophore represented by Formula (A):




wherein
X1, X2, X3, and X4 are independently selected from the group consisting of H, OH, halo, a C1-C4 alkyl group, and a C1-C3 alkoxy group; and
P1, P2, P3, P4, P5, Q1, Q2, Q3, Q4, and Q5 are independently selected from the group consisting of H, OH, CN, NO2, halo, a C1-C15 alkyl, and a C1-C15 alkoxy group.
As disclosed in Scheme 1 of US 2003/0203888 A1, a carbon-carbon double bond at β-position of one or two pyrrole rings of a porphyrin compound is reduced using oxmium tetraoxide as a catalyst to produce a chlorin compound and a bacteriochlorin compound. However, the bacteriochlorin compound prepared from the porphyrin compound in US 2003/0203888 A1 has no or only one substituent on each of the carbon atoms at positions 7, 8, 17, and 18 of a multi-cyclic core. In addition, it is indicated in the CRC Handbook of Organic Photochemistry and Photobiology, Volumes 1 & 2 (Second Edition, Sep. 29, 2003) by William M. Horspool et al., Page 144-3 that the bacteriochlorin compound prepared from the porphyrin compound via reduction is found to be air sensitive. The bacteriochlorin compound thus prepared is liable to be oxidized to the porphyrin compound or the chlorin compound, and may not be used for subsequent applications over a long period of time. The bacteriochlorin compound prepared from the porphyrin compound using oxmium tetraoxide as a catalyst, as disclosed in US 2003/0203888 A1, may similarly have the air sensitive problem.
U.S. Pat. No. 7,534,807 discloses a method of making a bacteriochlorin, which is carried out by condensing a pair of compounds of Formula II defined therein in an organic solvent and preferably in the presence of an acid.
SUMMARY
An object of the disclosure is to provide a bacteriochlorin-based organic dye which is stable in air.
According to the disclosure, there is provided a bacteriochlorin-based organic dye represented by Formula (II):




wherein
R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group;
Y1, Y2, Y3, and Y4 independently represent an alkyl group;
T1, T2, T3, and T4 are independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group;
Q2 is selected from the group consisting of a single bond,
































and





P2 represents an amino group or an anchoring group;
n represents 0 or 1; and
Z represents H,




or NR14R15,

wherein
P1 represents hydrogen, an electron-donating group, or an electron-withdrawing group,
m represents 0 or 1,
R14 and R15 are independently selected from the group consisting of hydrogen, a C1-C12 alkyl group, and




wherein R16 represents a C1-C12 alkyl group or a C1-C12 alkoxy group, and

Q1 is selected from the group consisting of a single bond,
























and





wherein A1 and A2 independently represent a C1-C12 alkyl group, and b represents an integer ranging from 1 to 4.



BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the disclosure will become apparent in the following detailed description of the embodiment (s) with reference to the accompanying drawings, of which:
FIG. 1 is a graph showing current density-voltage (J-V) curves of Compounds A2 and A4 obtained using a a solar simulator (AM 1.5G, SS50 AAAEM, PET, irradiance: 100 mW/cm2); and
FIG. 2 is a graph showing incident photon-to-current conversion efficiency (IPCE) spectra of solar cells sensitized with Compounds A2 and A4.



DETAILED DESCRIPTION
A bacteriochlorin-based organic dye of the disclosure is represented by Formula (II):




wherein
R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group;
Y1, Y2, Y3, and Y4 independently represent an alkyl group;
T1, T2, T3, and T4 are independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group;
Q2 is selected from the group consisting of a single bond,
































and





P2 represents an amino group or an anchoring group;
n represents 0 or 1; and
Z represents H,




or NR14R15,

wherein
P1 represents hydrogen, an electron-donating group, or an electron-withdrawing group,
m represents 0 or 1,
R14 and R15 are independently selected from the group consisting of hydrogen, a C1-C12 alkyl group, and




wherein R16 represents a C1-C12 alkyl group or a C1-C12 alkoxy group, and

Q1 is selected from the group consisting of a single bond,
























and





wherein A1 and A2 independently represent a C1-C12 alkyl group, and b represents an integer ranging from 1 to 4.
In the bacteriochlorin-based organic dye of the disclosure, there are two substituents on each of the carbon atoms at positions 7 and 17 of the bacteriochlorin core. The bacteriochlorin-based organic dye of the disclosure is stable in air, and thus may be used as a photosensitizer in a dye-sensitized solar cell.
In certain embodiments, Z represents




wherein P1, Q1, and m are defined as above.

In certain embodiments, P1 is selected from the group consisting of hydrogen, NR11R12, and a hydroxyl group, wherein R11 and R12 are independently selected from the group consisting of hydrogen, a C1-C12 alkyl group, and




wherein R13 represents a C1-C12 alkyl group or a C1-C12 alkoxy group. P2 is selected from the group consisting of —NH2, a carboxyl group, and a nitro group.

In certain embodiments, Q1 is selected from the group consisting of a single bond,








and





wherein A1 and A2 independently represent a C1-C12 alkyl group.

In certain embodiments, Q2 is selected from the group consisting of
















and





wherein b represents an integer ranging from 1 to 4.

In certain embodiments, m is 0. Q1 represents a single bond. P1 represents hydrogen or NR11R12, wherein R11 and R12 independently represent




wherein R13 represents a C1-C12 alkyl group or a C1-C12 alkoxy group.

In certain embodiments, the alkyl group for R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, Y1, Y2, Y3, Y4, T1, T2, T3, and T4 is a C6-C12 alkyl group. The alkoxy group for R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, T1, T2, T3, and T4 is a C6-C12 alkoxy group.
In certain embodiments, each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 represents hydrogen.
In certain embodiments, R1, R5, R6, and R10 independently represent an alkyl group or an alkoxy group. Each of R2, R3, R4, R7, R8, and R9 represents hydrogen.
In certain embodiments, each of T1, T2, T3, and T4 represents hydrogen.
In certain embodiments, T1, T2, T3, and T4 independently represent an alkyl group or an alkoxy group.
In certain embodiments, Z represents NR14R15.
In certain embodiments, each of R14 and R15 represents




wherein R16 represents a C1-C12 alkyl group or a C1-C12 alkoxy group.

In certain embodiments, Q2 is




P2 represents the anchoring group which is bonded to Q2 at a para position and which is selected from the group consisting of a carboxylic group and a hydroxamic group.

In certain embodiments, Q2 is




and P2 represents a carboxylic group bonded to Q2 at each of positions 3 and 5 of Q2.

In certain embodiments, the electron-withdrawing group is selected from the group consisting of








and





When the bacteriochlorin-based organic dye represented by Formula (II) of the disclosure is used as a photosensitizer for a dye-sensitized solar cell, Q1 and Q2 contained in Formula (II) may enhance the photoelectric conversion efficiency of the dye-sensitized solar cell.
In certain embodiments, when Z, P1, and/or P2 in Formula (II) represent(s) an amino group, the bacteriochlorin-based organic dye represented by Formula (II) of the disclosure may be formed into a film via polymerization or electro-polymerization. The film may be used, for example, for modifying an electrode surface.
Specifically,




is a chromophore. When a photosensitizer contains





the wavelength range of sunlight which may be absorbed by the photosensitizer may be increased. Therefore, the photoelectric conversion efficiency of the dye-sensitized solar cell may be increased.

When Q1 is




or





and P1 is a hydroxyl group, an enhanced anchoring group is formed on the photosensitizer such that the photosensitizer may be firmly and stably anchored onto a semiconductor. Therefore, the photoelectric conversion efficiency of the dye-sensitized solar cell may be enhanced in long-term use.





is an electron-withdrawing group, and may be used in combination with a proper electron-donating group to enhance an “electron push-pull effect” so as to enhance an effect of introduction of electrons from the photosensitizer to a semiconductor. Therefore, the photoelectric conversion efficiency of the dye-sensitized solar cell may be increased.













and





are rigid so as to enhance the chemical structure of the photosensitizer and have a high fluorescent quantum yield. Therefore, the life cycle of the photosensitizer may be extended, the probability of introduction of electrons from the photosensitized to the semiconductor may be increased, and the photoelectric conversion efficiency of the dye-sensitized solar cell may be increased.





is a conductive polymeric unit, and the excellent conductivity thereof may increase the photoelectric conversion efficiency of the dye-sensitized solar cell.

When P1, P2, Q1, Q2, m, and n are as shown in Table 1, the bacteriochlorin-based organic dye of the disclosure may be used as a photosensitizer for an n-type dye-sensitized solar cell.












TABLE 1





P1
Q1
m
n
Q2
P2







—H
Single bond
0
1




—COOH


 


—H
Single bond
0
1










 


—H
Single bond
0
1




—COOH


 


—H
Single bond
0
1




—COOH


 


—H
Single bond
0
1










 


—H
Single bond
0
1




—COOH


 


—N(C8H17)2




1
1




—COOH


 


—N(C8H17)2




1
1




—COOH


 


—N(C8H17)2




1
1










 


—N(C8H17)2




1
1




—COOH


 


—N(C8H17)2




1
1




—COOH


 


—N(C8H17)2




1
1










 


—N(C8H17)2




1
1




—COOH


 










1
1




—COOH


 










1
1










 










1
1




—COOH


 


—R11R12, wherein R11 and R12 represent   







1
1




—COOH


 


—R11R12, wherein R11 and R12 represent   







1
1










 


—R11R12, wherein R11 and R12 represent   







1
1




—COOH


 


—N(C8H17)2




1
1




—COOH


 


—N(C8H17)2




1
1










 


—N(C8H17)2




1
1




—COOH


 


—H




1
1




—COOH


 


—H




1
1










 


—H




1
1




—COOH


 


—H




1
1




—COOH


 


—H




1
1










 


—H




1
1




—COOH


 


—R11R12, wherein R11 and R12 represent   



Single bond
0
1




—COOH


 


—R11R12, wherein R11 and R12 represent   



Single bond
0
1










 


—R11R12, wherein R11 and R12 represent   



Single bond
0
1




—COOH


 


—R11R12, wherein R11 and R12 represent   



Single bond
0
1




—COOH


 


—R11R12, wherein R11 and R12 represent   



Single bond
0
1










 


—R11R12, wherein R11 and R12 represent   



Single bond
0
1




—COOH


 


—OH




1
1




—NO2


 


—OH




1
1




—NO2


 


—N(C8H17)2




1
0



   wherein b is an integer from 1 to 4
—COOH


 


—N(C8H17)2




1
0



   wherein b is an integer from 1 to 4






 


—R11R12, wherein R11 and R12 represent   



Single bond
0
0



   wherein b is an integer from 1 to 4
—COOH


 


—R11R12, wherein R11 and R12 represent   



Single bond
0
0



   wherein b is an integer from 1 to 4













When P1, P2, Q1, Q2, m, and n are as shown in Table 2, the bacteriochlorin-based organic dye of the disclosure may be used as an electropolymerization dye.












TABLE 2





P1
Q1
m
n
Q2
P2







—H
Single bond
0
1




—NH2


 


—N(C8H17)2




1
1




—NH2


 


—N(C8H17)2




1
1




—NH2


 


—H




1
1




—NH2


 


—R11R12, wherein R11 and R12 represent   



Single bond
0
1




—NH2


 


—NH2




1
1




—NO2


 


—NH2




1
1




—NO2









The bacteriochlorin-based organic dye represented by Formula (II) is derived from a bacteriochlorin-based compound represented by Formula (I):




wherein
R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group;
Y1, Y2, Y3, and Y4 independently represent an alkyl group; and
T1, T2, T3, and T4 are independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group.
The bacteriochlorin-based compound represented by Formula (I) may be prepared by subjecting a compound represented by Formula (I-1) below and a compound represented by Formula (I-2) below to a reaction in the presence of a solvent and a catalyst.




(wherein R1, R2, R3, R4, R5, Y1, Y2, T3, and T4 are as defined above)





(wherein R6, R7, R8, R9, R10, Y3, Y4, T1, and T2 are as defined above)
A non-limiting example of the solvent is acetonitrile (CH3CN). Anon-limiting example of the catalyst is boron trifluoride etherate (BF3.O(Et)2).
Examples of the disclosure will be described hereinafter. It is to be understood that these examples are exemplary and explanatory and should not be construed as a limitation to the disclosure.
Example 1
Preparation of a Bacteriochlorin-Based Compound







Preparation of Compound A1-1
Benzaldehyde (10 g, 94.33 mmol), nitro methane (250 mL), and ammonium acetate (2.179 g, 28.27 mmol) were added into a round bottom bottle to obtain a reaction mixture. The reaction mixture was heated under reflux for 3 hours to obtain a reaction product. The reaction product was cooled to 25° C., and was then dissolved in a proper volume amount of methylene chloride (CH2Cl2). The reaction product was then extracted by adding water in a volume amount equal to that of methylene chloride to obtain an organic phase. The organic phase was washed with an aqueous sodium chloride solution (NaCl(aq)), and was then dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 4:1 v/v mixture of n-hexane and methylene chloride as an eluent to obtain trans-β-nitrostyrene (Compound A1-1, 10.58 g, MW=149.15 g/mole, light yellow crystalline solid, yield: 75%). Spectrum analysis for Compound A1-1: 1H NMR (CDCl3, 300 MHz), δ (ppm): 7.43-7.53 (m, 5H); 7.58 (d, 2H, J=13.73 Hz); 7.99 (d, 1H, J=13.65 Hz). 13C NMR (CDCl3, 75 MHz): 129.2, 129.4, 130.1, 132.2, 137.1, 139.1.
Preparation of Compound A1-2
Pyrrole (1.08 g, 16.09 mmol) and Compound A1-1 (2 g, 13.41 mmol) were added to a round bottom bottle (100 mL), followed by addition of silica gel (70-230 mesh, 5 g) and homogeneous mixing to obtain a reaction mixture. The reaction mixture was subjected to a reaction in an oil bath at 150° C. for 2 minutes. Completion of the reaction was confirmed by thin layer chromatography (TLC). A reaction product thus obtained was purified by column chromatography on a silica gel column using a 9:1 v/v mixture of n-hexane and ethyl acetate as an eluent to obtain 2-(2-nitro-1-phenylethyl)-1H-pyrrole (Compound A1-2, 2.15 g, MW=216.24 g/mole, brown oil, yield: 75%). Spectrum analysis for Compound A1-2: 1H NMR (CDCl3, 300 MHz), δ (ppm): 4.77-4.83 (m, 1H); 4.87-5.00 (m, 2H); 6.11 (s, 1H); 6.18-6.20 (m, 2H); 6.68 (s, 1H); 4.77-4.83 (m, 1H); 7.24-7.26 (m, 2H); 7.30-7.40 (m, 3H); 7.93 (s, 1H). 13C NMR: (CDCl3, 75 MHz): 42.94, 79.23, 105.81, 108.66, 118.27, 127.96, 128.17, 128.95, 129.25, 138.03.
Preparation of Compound A1-3
Mesityl oxide (10 mL, 87.43 mmol), diphenyl diselenide (2.72 g, 8.74 mmol), and ammonium peroxydisulfate (59.83 g, 262.20 mmol) were added to anhydrous methanol (670 mL) to obtain a reaction mixture. The reaction mixture was heated under reflux in a nitrogen atmosphere for 4 hours. Completion of the reaction was confirmed by TLC. A reaction product thus obtained was added to water (1.20 L), and was then extracted using chloroform (CHCl3) to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate, followed by evacuation to obtain a dark brown oily coarse product. The coarse product was purified by column chromatography on a silica gel column using a 9.3:0.7 v/v mixture of n-hexane and ethyl acetate as an eluent to obtain 1,1-dimethoxy-4-methylpent-3-en-2-one (Compound A1-3, 4.2 g, MW=158.19 g/mole, light yellow oil, yield: 30%). Spectrum analysis for Compound A1-3: 1H NMR (CDCl3, 300 MHz), δ (ppm): 1.91 (s, 3H); 2.15 (s, 3H); 3.36 (s, 6H); 4.44 (s, 1H); 6.31 (s, 1H). 13C NMR (CDCl3, 75 MHz): 21.3, 28.2, 54.5, 104.5, 119.0, 160.3, 194.2.
Preparation of Compound A1-4
Compound A1-2 (2.04 g, 9.43 mmol) was mixed with Compound A1-3 (1.79 g, 11.32 mmol, 1.2 equiv.), followed by addition of 1,8-diazodicyclo[5.4.0]undec-7-ene (DBU, 4.22 mL, 28.98 mmol) to obtain a reaction mixture. The reaction mixture was subjected to a reaction at 25° C. in a nitrogen atmosphere for 16 hours to obtain a reaction product. The reaction product was added with a saturated ammonium chloride solution, and was then extracted using ethyl acetate to obtain an organic phase. The organic phase was washed using an aqueous sodium chloride solution, and was then dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 9:1 v/v mixture of n-hexane and ethyl acetate as an eluent to obtain 1,1-dimethoxy-4,4-dimethyl-5-nitro-6-phenyl-6-(1H-pyrrol-2-yl)hexan-2-one (Compound A1-4, 0.88 g, MW=374.43 g/mole, light brown solid, yield: 25%).
Preparation of Compound A1-5
Compound A1-4 (730 mg, 1.95 mmol) was dissolved in anhydrous tetrahydrofuran (THF, 3.00 mL) in a flask, followed by addition of sodium methoxide (CH3ONa, 316 mg, 5.85 mmol) to obtain a first reaction mixture. The first reaction mixture was subjected to a reaction at 25° C. in a nitrogen atmosphere for 1 hour to obtain a first reaction product. A TiCl3 solution (12.53 mL, 9.75 mmol, 5.0 equiv.) and water (30 mL) were added to another flask, followed by addition of ammonium acetate (NH4OAc, 37.58 g, 487.60 mmol) to obtain a buffer solution (pH=6.0). The TiCl3 solution was prepared by dissolving a 12 wt % solution of TiCl3 in a 10 wt % solution of HCl. The buffer solution was added with anhydrous THF (5 mL), followed by addition of the first reaction product to obtain a second reaction mixture. The second reaction mixture was subjected to a reaction at 25° C. in a nitrogen atmosphere for 16 hours to obtain a second reaction product, which was extracted using ethyl acetate to obtain an organic phase. The organic phase was washed using a 5% solution of sodium carbonate, and was then dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on an alumina column using a 95:5 v/v mixture of n-hexane and ethyl acetate as an eluent to obtain 2-[(5-(dimethoxymethyl)-3,3-dimethyl-3,4-dihydro-2H-pyrrol-2-ylidene) (phenyl)methyl]-1H-pyrrole (Compound A1-5, 107 mg, MW=324.42 g/mole, bright yellow solid, yield: 17%). Spectrum analysis for Compound A1-5: 1H NMR (CDCl3, 300 MHz), δ (ppm): 0.93 (s, 6H); 2.60 (s, 2H); 3.48 (s, 6H); 5.07 (s, 1H); 5.39 (s, 1H); 6.04-6.06 (m, 1H); 6.90 (s, 1H); 7.32-7.35 (m, 5H); 11.43 (s, 1H). 13C NMR (CDCl3, 75 MHz): 28.7, 29.7, 41.8, 50.5, 54.5, 102.7, 108.1, 111.2, 119.6, 127.2, 127.3, 131.2, 134.8, 137.3, 153.9, 173.3.
Preparation of Compound A1
Compound A1-5 (50 mg, 0.154 mmol) was dissolved in acetonitrile (CH3CN, 8.3 mL), followed by addition of boron trifluoride etherate (BF3.O(Et)2, 156 μL, 1.264 mmol) to obtain a reaction mixture, which was subjected to a reaction at 25° C. for 24 hours to obtain a reaction product. The reaction product was neutralized by adding triethylamine (Et3N, 176 μL, 1.264 mmol), followed by removal of organic solvents to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 1:1 v/v mixture of n-hexane and methylene chloride as an eluent to obtain Compound A1 (10.0 mg, MW=522.68 g/mole, yield: 37%). Spectrum analysis for Compound A1: 1H NMR (CDCl3, 300 MHz), δ (ppm): −1.60 (s, 2H); 1.56 (s, 12H); 4.40 (s, 4H); 7.58-7.69 (m, 6H); 7.90-7.94 (m, 6H); 8.55 (s, 2H); 8.83 (s, 2H). 13C NMR (CDCl3, 75 MHz): 29.7, 30.1, 47.3, 55.2, 99.5, 114.5, 122.2, 122.5, 126.3, 127.5, 133.8, 134.8, 138.8, 140.8, 156.2, 166.9.
Example 2
Preparation of a Bacteriochlorin-Based Organic Dye










Preparation of Compound A2-1
Methyl 4-iodobenzoate (1 g, 3.816 mmol), trimethylsilylacetylene (5 mL, 35.13 mmol, 9.24 equiv.), and triethylamine (15 mL) were added into a Schlenk flask, followed by addition of anhydrous THF (15 mL) as a solvent to obtain a mixture. The mixture was degassed using a freeze/thaw cycle (three times), and was then added with Pd(PPh3)2Cl2 (133.94 mg, 5 mol %) and copper (I) iodide (CuI, 36.34 mg, 5 mol %) within a water-free and oxygen-free glove box to obtain a reaction mixture, which was subjected to a reaction in an oil bath at 50° C. for 20 hours to obtain a reaction product. The reaction product was concentrated under reduced pressure to remove THF and triethylamine, and was dissolved in a proper volume amount of methylene chloride, followed by extraction using NH4Cl(aq) in a volume amount equal to that of methylene chloride to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 9:1 v/v mixture of n-hexane and ethyl acetate as an eluent to obtain methyl 4-trimethylsilyl ethynyl benzoate (Compound A2-1, 878 mg, MW=232.35 g/mole, white solid, yield: 98.5%). Spectrum analysis for Compound A2-1: 1H NMR (CDCl3, 300 MHz), δ (ppm): 0.25 (s, 9H); 3.90 (s, 3H); 7.50 (d, 2H, J=8.43 Hz); 7.95 (d, 2H, J=8.43 Hz). 13C NMR (CDCl3, 75 MHz): −0.2, 52.2, 97.7, 104.1, 127.8, 129.4, 129.7, 131.9, 166.5.
Preparation of Compound A2-2
Compound A2-1 (250 mg, 1.08 mmol) was dissolved in a mixture of anhydrous THF (7.5 mL) and methanol (7.5 mL), followed by adding K2CO3 to obtain a reaction mixture, which was then subjected to a reaction at 25° C. in a nitrogen atmosphere for 1 hour to obtain a reaction product. The reaction product was added with a saturated aqueous NaHCO3 solution, followed by extraction using methylene chloride to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 9:1 v/v mixture of n-hexane and ethyl acetate as an eluent to obtain methyl 4-ethynylbenzoate (Compound A2-2, 160 mg, MW=160.17 g/mole, yield: 93.0%). Spectrum analysis for Compound A2-2: 1H NMR (CDCl3, 300 MHz), δ (ppm): 3.23 (s, 1H); 3.92 (s, 3H); 7.55 (d, 2H, J=8.27 Hz); 7.99 (d, 2H, J=8.27 Hz). 13C NMR (CDCl3, 75 MHz): 52.3, 80.1, 82.8, 129.5, 132.1, 166.4.
Preparation of Compound A2-3
Compound A1 (100 mg, 0.19 mmol) was dissolved in anhydrous THF (20 mL), followed by adding N-bromosuccinimide (NBS, 34 mg, 0.19 mmol) to obtain a reaction mixture, which was subjected to a reaction at 25° C. for 10 minutes to obtain a reaction product. The reaction product was added with CH2Cl2 (10 mL), and was then washed using an aqueous NaHCO3 solution. An organic phase thus obtained was dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 1:1 v/v mixture of n-hexane and methylene chloride as an eluent to obtain Compound A2-3 (98 mg, MW=601.58 g/mole, yield: 85%). Spectrum analysis for Compound A2-3: 1H NMR (CDCl3, 300 MHz), δ (ppm): −1.44 (d, 2H, J=13.86 Hz); 1.51 (d, 1H, J=2.81 Hz); 4.31 (s, 2H); 4.49 (s, 2H); 7.56 ̃7.68 (m, 6H); 7.79 ̃7.91 (m, 6H); 8.50 (d, 1H, J=3.74 Hz); 8.68 (s, 1H); 8.90 (d, 2H, J=4.52 Hz). 13C NMR (d8-THF, 150 MHz) 171.1, 165.9, 160.4, 155.5, 141.8, 141.4, 141.3, 138.8, 138.2, 134.9, 134.5, 133.2, 131.6, 129.6, 128.6, 128.5, 127.3, 127.2, 125.8, 125.4, 123.0, 122.1, 117.4, 115.3, 101.2, 100.4, 59.2, 56.3, 54.9, 48.2, 47.4, 39.9, 31.4, 30.6, 30.3, 29.9, 24.7, 23.9, 14.4, 11.3. MALDI-TOF: calc'd for C36H33BrN4 600. 19[M+]. found 601.49 [MH]+.
Preparation of Compound A2-4
Compound A2-3 (10 mg, 12.91 μmol), Compound A2-2 (4.14 mg, 25.82 μmol, 2.23 equiv.), and triethylamine (1 mL) were added into a Schlenk flask, followed by addition of anhydrous THF (10 mL) as a solvent to obtain a mixture. The mixture was degassed using a freeze/thaw cycle (three times), and was then added with Pd(PPh3)2Cl2 (2.27 mg, 30 mol %) and AsPh3 (9.49 mg, 2.4 equiv.) within a water-free and oxygen-free glove box to obtain a reaction mixture, which was subjected to a reaction in an oil bath at 50° C. for 20 hours to obtain a reaction product. The reaction product was concentrated under reduced pressure to remove THF and triethylamine, and was then dissolved in a proper volume amount of methylene chloride, followed by extraction using NH4Cl(aq) in a volume amount equal to that of methylene chloride to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 1:1 v/v mixture of n-hexane and methylene chloride as an eluent to obtain Compound A2-4 (8.3 mg, MW=680.84 g/mole, pink solid, yield: 75%). Spectrum analysis for Compound A2-4: 1H NMR (CDCl3, 300 MHz), δ (ppm): −1.28 (s, 1H); −1.21 (s, 1H); 1.57 (s, 12H); 3.98 (s, 3H); 4.32 (s, 2H); 4.63 (s, 2H); 7.58-7.69 (m, 6H); 7.88-7.93 (m, 8H); 8.14 (d, 2H, J=8.25 Hz); 8.49 (d, 1H, J=3.39 Hz); 8.74 (s, 1H); 9.07 (d, 2H, J=4.12 Hz)
Preparation of Compound A2
Compound A2-4 (20 mg, 29.38 μmol) was dissolved in a mixture of THF (14 mL) and methanol (7 mL), followed by addition of an aqueous NaOH solution (8 mL, 2.5 N) to obtain a reaction mixture, which was then subjected to a reaction at 25° C. for 1 hour to obtain a reaction product. The reaction product was neutralized by adding an aqueous HCl solution (1N), followed by extraction using methylene chloride to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 1:9 v/v mixture of methanol and methylene chloride as an eluent to obtain Compound A2 (17 mg, MW=666.81 g/mole, pink solid, yield: 90.0%). Spectrum analysis for Compound A2: 1H NMR (CDCl3, 300 MHz): −1.29 (s, 1H); −1.23 (s, 1H); 1.54 (d, 12H, J=14.91 Hz); 4.31 (s, 2H); 4.64 (s, 2H); 7.55 ̃7.67 (m, 6H); 7.87-7.96 (m, 86H); 8.24 (d, 2H, J=8.12 Hz); 8.48 (d, 1H, J=4.85 Hz); 8.60 (s, 1H); 8.73 (s, 1H); 9.08 (d, 2H, J=4.63 Hz).
Example 3
Preparation of a Bacteriochlorin-Based Organic Dye




Compound A2-3 (42.1 mg, 0.070 mmol) and 4-ethynylaniline (16.4 mg, 0.14 mmol; for the synthesis method therefor, reference may be made to Dalton Trans., 2005, pp. 396-401) were dissolved in anhydrous THF (40 mL), followed by addition of triethylamine (5 mL) to obtain a mixture. The mixture was degassed using a freeze/thaw cycle (three times), and was then added with Pd(PPh3)2Cl2 (14.74 mg, 30 mol %) and AsPh3 (51.43 mg, 2.4 equiv.) within a water-free and oxygen-free glove box to obtain a reaction mixture, which was subjected to a reaction in an oil bath at 50° C. for 17 hours to obtain a reaction product. The reaction product was concentrated under reduced pressure to remove THF and triethylamine, and was then dissolved in a proper volume amount of methylene chloride, followed by extraction using NH4Cl(aq) in a volume amount equal to that of methylene chloride to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 1:1 v/v mixture of n-hexane and methylene chloride as an eluent to obtain a purified product, which was dissolved in THF, followed by recrystallization by adding a proper amount of methanol, thereby obtaining Compound A3 (30.1 mg, MW=637.81 g/mole, purple solid, yield: 67%). Spectrum analysis for Compound A3: 1H NMR: (CDCl3, 300 MHz) −1.28 (d, 2H, J=12.24 Hz); 1.53 (d, 12H, J=9.33 Hz); 3.89 (s, 2H); 4.31 (s, 2H); 4.60 (s, 2H); 6.77 (d, 2H, J=6.77 Hz); 7.56-7.66 (m, 8H); 7.84-7.89 (m, 6H); 8.47 (dd, 1H, J=4.53 Hz, J=1.80 Hz); 8.71 (s, 1H); 9.07 (dd, 1H, J=4.67 Hz, J=2.19 Hz). 13C NMR: CDCl3, 75 MHz) 168.1, 167.1, 160.7, 158.1, 150.2, 142.1, 142.0, 140.1, 139.2, 136.9, 136.7, 134.9, 134.8, 133.5, 128.6, 127.4, 123.9, 123.6, 123.1, 122.5, 116.9, 116.2, 115.0, 113.0, 112.7, 101.0, 98.4, 98.0, 91.3, 57.2, 56.0, 48.0, 47.6, 31.0, 30.4. Elemental analysis: calc'd for C44H39N5.0.5H2O: C, 81.70%, H, 6.23%, N, 10.83%. found: C, 81.66%, H, 6.08%, N, 10.75%. MALDI-TOF: calc'd for C44H39N5 637.32 [M+]. found 637.18 [M+].
Example 4
Preparation of a Bacteriochlorin-Based Organic Dye
















Preparation of Compound A4-1
Compound A2-3 (10 mg, 16.62 μmol), triisopropylsilylacetylene ((TIPS)-acetylene, 37 μL, 0.71 mmol), and triethylamine (1 mL) were added to anhydrous THF (10 mL) to obtain a mixture. The mixture was degassed using a freeze/thaw cycle (three times), and was then added with Pd(PPh3)2Cl2 (3.5 mg, 4.49 μmol, 30 mol %) and AsPh3 (12.2 mg, 39.89 μmol, 2.4 equiv.) within a water-free and oxygen-free glove box to obtain a reaction mixture, which was subjected to a reaction in an oil bath at 50° C. for 22 hours to obtain a reaction product. The reaction product was concentrated under reduced pressure to remove THF and triethylamine, and was dissolved in a proper volume amount of methylene chloride, followed by extraction using NH4Cl(aq) in a volume amount equal to that of methylene chloride to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 7:3 v/v mixture of n-hexane and methylene chloride as an eluent to obtain a purified product, which was dissolved in methylene chloride, followed by recrystallization by adding a proper amount of methanol, thereby obtaining Compound A4-1 (10.5 mg, MW=703.04 g/mole, pinkish green solid, yield: 90%). Spectrum analysis for Compound A4-1: 1H NMR: (CDCl3, 300 MHz) −1.36 (s, 2H); 1.34 (s, 21H); 1.52 (d, 12H, J=2.4 Hz); 1.57 (s, 6H); 4.32 (s, 2H); 4.55 (s, 2H); 7.56-7.67 (m, 6H); 7.84-7.91 (m, 6H); 8.48 (d, 1H, J=2.7 Hz); 8.73 (s, 1H); 9.06 (d, 2H, J=2.7 Hz). MASS (MALDI-TOF): m/z calculated for C47H54N4Si 703.04 [M]+, obtained m/z 704.56[MH]+.
Preparation of Compound A4-2
Compound A4-1 (100 mg, 0.14 mmol) was dissolved in anhydrous THF (120 mL), followed by addition of a solution of N-bromosuccinimide (NBS, 25.32 mg, 0.14 mmol) in anhydrous THF (10 mL) with magnetic stirring to obtain a reaction mixture. The reaction mixture was subjected to a reaction at 25° C. for 3 minutes, and was analyzed by TLC, which indicated 50% residual reactant. A solution of NBS (12.66 mg, 0.07 mmol) in anhydrous THF (5 mL) was further added, and the reaction was performed at 25° C. for additional 3 minutes. Analysis by TLC indicated that the reaction was complete. A reaction product produced thereby was added with acetone (10 mL), and was then evacuated to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 1:1 v/v mixture of n-hexane and methylene chloride as an eluent to obtain a purified product, which was dissolved in methylene chloride, followed by recrystallization by adding a proper amount of methanol, thereby obtaining Compound A4-2 (67 mg, MW=781.94 g/mole, pink solid, yield: 61%). Spectrum analysis for Compound A4-2: 1H NMR: (CDCl3, 300 MHz) −1.18 (s, 2H); 1.26 (s, 3H); 1.32 (s, 18H); 1.48 (s, 12H); 4.42 (s, 2H); 4.47 (s, 2H); 7.52-7.67 (m, 6H); 7.70-7.73 (m, 1H); 7.82-7.88 (m, 5H); 8.83 (d, 1H, J=2.64 Hz); 9.01 (d, 1H, J=3.00 Hz). 13C NMR: (d8-THF, 150 MHz) 170.4, 166.8, 163.3, 156.7, 141.5, 141.3, 140.3, 139.8, 139.3, 134.7, 134.6, 134.6, 133.9, 128.8, 128.6, 127.4, 127.3, 127.2, 126.0, 124.1, 123.8, 123.2, 117.8, 117.6, 110.7, 101.9, 99.3, 97.6, 96.3, 58.9, 57.4, 48.0, 47.0, 30.7, 30.7, 30.6, 30.5, 19.4, 12.6.
Preparation of Compound A4-3
Compound A4-2 (50 mg, 63.94 μmol) and 4-ethynyl-N,N-dioctylaniline (43.68 mg, 0.128 mmol; for the synthesis method therefor, reference may be made to Energy Environ. Sci., 2012, 5, pp. 6933-6940) were dissolved in anhydrous THF (50 mL), followed by addition of triethylamine (5 mL) to obtain a mixture. The mixture was degassed using a freeze/thaw cycle (three times), and was then added with Pd(PPh3)2Cl2 (13.46 mg, 19.18 μmol, 30 mol %) and AsPh3 (46.99 mg, 153.46 μmol, 2.4 equiv) within a water-free and oxygen-free glove box to obtain a reaction solution, which was subjected to a reaction in an oil bath at 50° C. for 48 hours to obtain a reaction product. The reaction product was concentrated under reduced pressure to remove THF and triethylamine, and was dissolved in a proper volume amount of methylene chloride, followed by extraction using NH4Cl(aq) in a volume amount equal to that of methylene chloride to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 4:1 v/v mixture of n-hexane and methylene chloride as an eluent to obtain a purified product, which was dissolved in methylene chloride, followed by recrystallization by adding a proper amount of methanol, thereby obtaining Compound A4-3 (63 mg, MW=1042.60 g/mole, dark blue solid, yield: 94.5%). Spectrum analysis for Compound A4-3: 1H NMR: (CDCl3, 300 MHz) −0.9 (s, 2H); 0.91 (t, 6H, 6.87 Hz); 1.26-1.35 (m, 39H); 1.50 (d, 12H, J=5.50 Hz); 1.56 (s, 6H); 3.33 (t, 4H, J=7.66 Hz); 4.49 (d, 4H, J=16.16 Hz); 6.70 (d, 2H, J=8.83 Hz); 7.57-7.68 (m, 8H); 7.79 (s, 2H); 7.86 (d, 4H, J=7.62 Hz); 8.94 (d, 1H, J=3.14 Hz); 9.00 (d, 1H, J=3.32 Hz). 13C NMR: (CDCl3, 75 MHz) 167.3, 166.6, 161.1, 161.0, 147.9, 140.7, 138.7, 138.2, 137.1, 136.6, 133.8, 132.7, 127.6, 126.4, 123.2, 123.1, 122.3, 121.7, 116.8, 116.0, 111.5, 110.0, 109.8, 97.9, 97.7, 96.9, 96.0, 90.7, 56.2, 55.9, 51.1, 46.5, 46.4, 31.9, 30.5, 29.5, 29.4, 27.3, 27.2, 22.7, 19.0, 14.2, 11.8. MASS (MALDI-TOF): m/z calculated for C71H91N5Si [M]+ 1041.70, obtained m/z 1041.77[M]+.
Preparation of Compound A4-4
Compound A4-3 (50 mg, 47.96 μmol) was dissolved in anhydrous THF (50 mL), followed by addition of a 1M solution of tetra-n-butylammonium fluoride (TBAF, 47.96 μL, 47.96 μmol) to obtain a reaction mixture, which was subjected to a reaction at 0° C. with stirring in darkness for 1 hour to obtain a reaction product. The reaction product was concentrated under reduced pressure to remove THF, and was dissolved in a proper volume amount of methylene chloride, followed by extraction (twice) using water in a volume amount equal to that of methylene chloride to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 1:1 v/v mixture of n-hexane and methylene chloride as an eluent to obtain Compound A4-4 (35 mg, MW=886.26 g/mole, dark blue solid, yield: 82.7%). Spectrum analysis for Compound A4-4: 1H NMR: (CDCl3, 300 MHz) −0.94 (s, 2H); 0.91 (t, 4H, J=6.87 Hz); 1.26-1.35 (m, 46H); 1.50 (d, 12H, J=5.50 Hz); 1.64 (s, 4H); 3.32 (t, 4H, J=7.66 Hz); 4.49 (d, 4H, J=16.16 Hz); 6.70 (d, 2H, J=8.83 Hz); 7.57-7.68 (m, 8H); 7.79 (s, 2H); 7.86 (d, 4H, J=7.62 Hz); 8.94 (d, 1H, J=3.30 Hz); 9.00 (d, 2H, J=4.50 Hz). 13C NMR: (CDCl3, 75 MHz) 167.8, 166.5, 161.1, 160.9, 148.0, 140.6, 139.0, 138.1, 136.9, 136.7, 133.8, 133.7, 132.7, 127.7, 126.4, 123.3, 123.2, 122.7, 121.4, 117.0, 115.9, 111.5, 111.3, 109.7, 98.1, 97.9, 94.1, 90.6, 86.7, 82.8, 56.0, 55.7, 51.1, 46.7, 46.4, 31.9, 30.5, 30.4, 29.5, 29.4, 27.3, 27.2, 22.7, 14.2. MASS (MALDI-TOF): m/z calculated for C62H71N5 [M]+ 885.57, obtained m/z 886.531[MH]+.
Preparation of Compound A4-5
Compound A4-4 (92 mg, 93.65 μmol) and methyl-4-bromobenzoate (49.08 mg, 0.187 mmol) were dissolved in anhydrous THF (9 mL), followed by addition of triethylamine (9 mL) to obtain a mixture. The mixture was degassed using a freeze/thaw cycle (three times), and was then added with Pd2(dba)3 (25.73 mg, 28.10 μmol, 30 mol %) and AsPh3 (68.83 mg, 224.76 μmol) within a water-free and oxygen-free glove box to obtain a reaction mixture, which was subjected to a reaction in an oil bath at 50° C. for 22 hours to obtain a reaction product. The reaction product was concentrated under reduced pressure to remove THF and triethylamine, and was dissolved in a proper volume amount of methylene chloride, followed by extraction using NH4Cl(aq) in a volume amount equal to that of methylene chloride to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 1:1 v/v mixture of n-hexane and methylene chloride as an eluent to obtain Compound A4-5 (90.45 mg, MW=1020.39 g/mole, dark blue solid, yield: 94.65%). Spectrum analysis for Compound A4-5: 1H NMR: (CDCl3, 300 MHz) −0.85 (d, 2H, d, J=9.75 Hz); 0.90 (t, 6H, 6.54 Hz); 1.25-1.35 (m, 22H); 1.52 (d, 12H, J=6.44 Hz); 1.61 (s, 6H); 3.33 (t, 4H, J=7.37 Hz); 3.97 (s, 3H); 4.53 (d, 4H, J=7.67 Hz); 6.70 (d, 2H, J=8.53 Hz); 7.57-7.67 (m, 8H); 7.81 (s, 2H); 7.87 (d, 6H, J=6.09 Hz); 8.13 (d, 2H, J=8.40 Hz); 8.94 (d, 1H, J=3.48 Hz); 9.01 (d, 1H, J=3.47 Hz). 13C NMR: (CDCl3, 75 Hz) 167.7, 166.8, 166.5, 161.3, 160.7, 148.0, 140.5, 139.1, 138.1, 136.8, 136.4, 133.8, 133.7, 132.7, 131.1, 129.8, 129.2, 128.9, 127.7, 126.4, 123.4, 123.1, 122.7, 121.1, 117.3, 116.1, 111.5, 111.3, 109.6, 98.3, 98.1, 96.7, 95.1, 94.9, 90.6, 55.9, 55.6, 52.3, 51.1, 46.7, 46.4, 31.9, 30.4, 29.5, 29.4, 27.3, 27.2, 22.7, 14.1. MASS (MALDI-TOF): m/z calculated for C70H77N5O2 1019.61 [M]+, obtained m/z 1020.63[MH]+.
Preparation of Compound A4
Compound A4-5 (180 mg, 17.64 mmol) was dissolved in a mixture of THF (100 mL) and methanol (100 mL), followed by addition of an aqueous NaOH solution (2.5 N, 100 mL) to obtain a reaction mixture. The reaction mixture was subjected to a reaction at 25° C. for 1 hour, followed by addition of an aqueous HCl solution (1 N) until a pH value of 3 was reached. A reaction product thus obtained was concentrated under reduced pressure to remove the solvents, and was dissolved in a proper volume amount of methylene chloride, followed by extraction (twice) using water in a volume amount equal to that of methylene chloride to obtain an organic phase. The organic phase was dried using anhydrous sodium sulfate, followed by evacuation to obtain a coarse product. The coarse product was purified by column chromatography on a silica gel column using a 9:1 v/v mixture of methanol and chloroform as an eluent to obtain Compound A4 (110 mg, MW=1006.37 g/mole, dark blue solid, yield: 62%). Spectrum analysis for Compound A4: 1H NMR: (d8-THF, 600 MHz) −0.84 (d, 2H, J=15.15 Hz); 0.91 (t, 6H, J=6.81 Hz); 1.33-1.39 (m, 6H); 1.53 (d, 12H, J=9.07 Hz); 1.62-1.68 (m, 6H); 3.38-3.41 (m, 4H); 4.55 (s, 2H); 4.60 (s, 2H); 6.76 (d, 2H, J=8.66 Hz); 7.61-7.69 (m, 8H); 7.80-7.82 (m, 2H); 7.90-7.93 (m, 6H); 8.14 (d, 2H, J=8.20 Hz); 8.99-9.01 (m, 2H). 13C NMR: (d8-THF, 150 MHz) 168.3, 167.2, 161.7, 161.5, 149.0, 141.6, 139.8, 139.0, 137.5, 137.3, 134.7, 134.6, 133.4, 131.7, 130.7, 128.6, 127.3, 127.2, 123.9, 123.8, 123.2, 121.9, 118.2, 117.1, 112.4, 110.8, 99.3, 99.3, 96.6, 96.2, 95.9, 91.1, 56.8, 56.5, 51.7, 47.5, 47.2, 32.8, 30.7, 30.6, 30.5, 30.3, 28.2, 28.0, 23.5, 14.4.
Property Evaluation:
1. Maximum Absorption Wavelength and Molar Extinction Coefficient:
The maximum absorption wavelength (λmax, nm) and molar extinction coefficient (ε, 10−3M−1cm−1) of a compound were determined using an Agilent 8453 UV-Vis spectrophotometer. Each of samples obtained from Compound A1 (Example 1), Compound A2 (Example 2), and Compound A4 (Example 4) was dissolved in THF, and was determined at 298 K in a concentration range from 10−5 M to 10−6 M and in a wavelength range from 300 nm to 1100 nm.
2. Maximum Emission Wavelength:
The maximum emission wavelength (λmax, nm) of a compound was determined using an Agilent Eclipse fluorescence spectrophotometer. A sample obtained from Compound A1 (Example 1) was dissolved in THF, and was determined at 298 K at an excitation wavelength of 370 nm. A sample obtained from Compound A2 (Example 2) was dissolved in THF, and was determined at 298 K at an excitation wavelength of 372 nm. A sample obtained from Compound A4 (Example 4) was dissolved in THF, and was determined at 298 K at an excitation wavelength of 388 nm. These determinations were performed at a concentration of 2×10−6 M in a wavelength range from 390 nm to 900 nm at a scan speed of 600 nm/min.
3. Performances of Dye-Sensitized Solar Cell:
Since the configuration and manufacture of a dye-sensitized solar cell are well known in the art, only a brief description thereof is provided below.
A dye-sensitized solar cell includes an electrolyte, an anode, and a cathode. In the dye-sensitized solar cell illustrated in the disclosure, the electrolyte is composed of a 1 M solution of 1-methyl 3-propyl imidazolium iodide (PMII), a 0.05 M solution of I2, a 0.2 M solution of lithium iodide (LiI), and a 0.5 M solution of tert-butyl pyridine (TBP). The cathode is made from platinum. The anode is composed of four transparent active layers of TiO2 (manufactured by Eternal Chemical, particle size distribution: 20 nm to 40 nm), two scattering layers of TiO2 (manufactured by Eternal Chemical, particle size distribution: 300 nm to 400 nm), and the bacteriochlorin-based organic dye of the disclosure used as a photosensitizer. The anode was made by immersing a laminate formed from the four transparent active layers and the two scattering layers in a 0.1 mM solution of the bacteriochlorin-based organic dye of the disclosure in THF for 6 hours.
The open-circuit voltage, short-circuit current, fill factor, and photoelectric conversion efficiency of the dye-sensitized solar cell were determined using a solar simulator (AM 1.5G, SS50 AAAEM, PET) and a source meter (Keithley 2400). The dye-sensitized solar cell having a size of 0.4 cm×0.4 cm was placed at a measurement position where the dye-sensitized solar cell could be irradiated by the solar simulator, and was scanned at a scan range from −0.1 V to 0.8 V with a scan pitch of 0.02 V. A photocurrent versus voltage (I-V) curve measurement software (Forter, FIVMAS) was used to determine the open-circuit voltage, the short-circuit current, the fill factor, and the photoelectric conversion efficiency of the dye-sensitized solar cell.
4. Incident Photon-to-Electron Conversion Efficiency (IPCE):
Determination of incident photon-to-current conversion efficiency (IPCE) was performed by a 7-SCSpec system (Sofn Instruments Co., Ltd.) with an xenon lamp (7ILT250A, Sofn Instruments Co., Ltd.), a tungsten-halogen lamp (7ILT250A, Sofn Instruments Co., Ltd.), and a source meter (Keithley 2000). After spectrum calibration, the dye-sensitized solar cell was placed at a measurement position where the dye-sensitized solar cell may be irradiated by the lamps, was scanned at a scan range from 300 nm to 900 nm with a scan pitch of 10 nm to obtain a spectrum of IPCE, which was integrated to obtain a theoretical short-circuit current density.











TABLE 3









Emission




UV absorption spectrum
spectrum




wavelength/Log ε
λmax 




(nm/M−1cm−1)
(nm)




















Ex. 1
348/5.57
724



(Compound A1)
370/5.70





503/5.15





718/5.52




Ex. 2
372/5.38
749



(Compound A2)
551/5.01





745/5.36




Ex. 4
388/5.22
774



(Compound A4)
576/4.65





615/4.69





701/4.21





769/5.19



















TABLE 4








IPCE
Photoelectric conversion performances













integrated
short-circuit
Open-

photoelectric



current
current
circuit

conversion


Dye-
density from
density
voltage
Fill
efficiency


sensitized
the spectrum
(Jsc)
(Voc)
factor
(η)


solar cell
(mA cm−2)
(mA cm−2)
(V)
(FF)
(%)





Ex. 2
10.29
12.58
0.53
0.70
4.67


(Compound 







A2)







Ex. 4
14.99
16.13
0.52
0.64
5.36


(Compound 







A4)









Current density-voltage (J-V) curves of Compounds A2 and A4 obtained under irradiance of 100 mW/cm2 are shown in FIG. 1. IPCE spectra of solar cells sensitized with Compounds A2 and A4 are shown in FIG. 2
Compound A1 prepared in Example 1 has two methyl gropus on each of the carbon atoms at positions 7 and 17 of the bacteriochlorin core, and is thus stable in air. Therefore, Compound A1 may be used to prepare Compounds A2 and A4 in Examples 2 and 4, i.e., the bacteriochlorin-based organic dyes. As shown in Table 4, the bacteriochlorin-based organic dyes prepared in Examples 2 and 4 have satisfactory photoelectric conversion performances.
In fact, we observed that the compounds prepared in the illustrated examples were not oxidized to corresponding chlorin or porphyrin compounds during synthesis and purification thereof, preparation of a solar cell made therefrom, and measurement of properties thereof. The procedures for the synthesis, purification, preparation, and measurement are often carried out in air at room or elevated temperatures for hours, days, or weeks.
In view of the aforesaid, the bacteriochlorin-based organic dye of the disclosure may be stably prepared from a bacteriochlorin-based compound which has two substituents on each of the carbon atoms at positions 7 and 17 of the bacteriochlorin core. Therefore, the bacteriochlorin-based organic dye of the disclosure is stable in air, and may be used as a photosensitizer in dye-sensitized solar cell.
In the description above, for the purposes of explanation, numerous specific details have been set forth in order to provide a thorough understanding of the embodiment(s). It will be apparent, however, to one skilled in the art, that one or more other embodiments may be practiced without some of these specific details. It should also be appreciated that reference throughout this specification to “one embodiment,” “an embodiment,” an embodiment with an indication of an ordinal number and so forth means that a particular feature, structure, or characteristic may be included in the practice of the disclosure. It should be further appreciated that in the description, various features are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of various inventive aspects.
While the disclosure has been described in connection with what is (are) considered the exemplary embodiment(s), it is understood that this disclosure is not limited to the disclosed embodiment(s) but is intended to cover various arrangements included within the spirit and scope of the broadest interpretation so as to encompass all such modifications and equivalent arrangements.

## Claims

1. A bacteriochlorin-based organic dye represented by Formula (II):



wherein
R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group;
Y1, Y2, Y3, and Y4 independently represent an alkyl group;
T1, T2, T3, and T4 are independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group;
Q2 is selected from the group consisting of a single bond,

































and



P2 represents an amino group or an anchoring group;
n represents 0 or 1; and
Z represents H,





or NR14R15,
wherein
P1 represents hydrogen, an electron-donating group, or an electron-withdrawing group,
m represents 0 or 1,
R14 and R15 are independently selected from the group consisting of hydrogen, a C1-C12 alkyl group, and





wherein R16 represents a C1-C12 alkyl group or a C1-C12 alkoxy group, and
Q1 is selected from the group consisting of a single bond,

























and



wherein A1 and A2 independently represent a C1-C12 alkyl group, and b represents an integer ranging from 1 to 4.

2. The bacteriochlorin-based organic dye according to claim 1, wherein Z represents

3. The bacteriochlorin-based organic dye according to claim 2, wherein
P1 is selected from the group consisting of hydrogen, NR11R12, and a hydroxyl group, wherein R11 and R12 are independently selected from the group consisting of hydrogen, a C1-C12 alkyl group, and





wherein R13 represents a C1-C12 alkyl group or a C1-C12 alkoxy group; and
P2 is selected from the group consisting of —NH2, a carboxyl group, and a nitro group.

4. The bacteriochlorin-based organic dye according to claim 2, wherein
Q1 is selected from the group consisting of a single bond,









and




wherein A1 and A2 independently represent a C1-C12 alkyl group.

5. The bacteriochlorin-based organic dye according to claim 2, wherein Q2 is selected from the group consisting of
















and




wherein b represents an integer ranging from 1 to 4.

6. The bacteriochlorin-based organic dye according to claim 2, wherein
m is 0;
Q1 represents a single bond; and
P1 represents hydrogen or NR11R12, wherein R11 and R12 independently represent





wherein R13 represents a C1-C12 alkyl group or a C1-C12 alkoxy group.

7. The bacteriochlorin-based organic dye according to claim 2, wherein said alkyl group for R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, Y1, Y2, Y3, Y4, T1, T2, T3, and T4 is a C6-C12 alkyl group, and said alkoxy group for R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, T1, T2, T3, and T4 is a C6-C12 alkoxy group.

8. The bacteriochlorin-based organic dye according to claim 2, wherein each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 represents hydrogen.

9. The bacteriochlorin-based organic dye according to claim 2, wherein R1, R5, R6, and R10 independently represent an alkyl group or an alkoxy group, and each of R2, R3, R4, R7, R8, and R9 represents hydrogen.

10. The bacteriochlorin-based compound according to claim 2, wherein each of T1, T2, T3, and T4 represents hydrogen.

11. The bacteriochlorin-based compound according to claim 2, wherein T1, T2, T3, and T4 independently represent an alkyl group or an alkoxy group.

12. The bacteriochlorin-based compound according to claim 1, wherein Z represents NR14R15.

13. The bacteriochlorin-based compound according to claim 12, wherein each of R14 and R15 represents




wherein R16 represents a C1-C12 alkyl group or a C1-C12 alkoxy group.

14. The bacteriochlorin-based compound according to claim 1, wherein Q2 is




and P2 represents said anchoring group which is bonded to Q2 at a para position and which is selected from the group consisting of a carboxylic group and a hydroxamic group.

15. The bacteriochlorin-based compound according to claim 1, wherein Q2 is




and P2 represents a carboxylic group bonded to Q2 at each of positions 3 and 5 of Q2.

16. The bacteriochlorin-based compound according to claim 1, wherein said electron-withdrawing group is selected from the group consisting of








and