TW201223954A - Photosensitizer dyes and application of the same - Google Patents

Abstract

The present invention provides a ruthenium (Ru) complex represented by the following general formula (I), Wherein the definitions of X1, X2, Y1 to Y3, Z1, Z2 and m are shown above. The ruthenium (Ru) complexes can be used as photosensitizers for dye-sensitized solar cells which display excellent power-conversion efficiencies (9.5% for one of our compounds; compared to commercial N3, 8.8%).

Description

201223954 VI. Description of the Invention: [Technical Field] The present invention relates to a photosensitizer for a dye-sensitized solar cell. Still further, the present invention relates to novel sensitizers for use in dye-sensitized solar cells. [Prior Art] In view of the rising oil prices year after year, the development of alternative energy sources has become an important research topic. Solar energy is an energy source other than the surface of the earth. Its global average annual convertible energy is estimated to be 120,000 TW. It is an inexhaustible clean energy source that can meet the needs of the whole world. Therefore, the solar energy source that can be used effectively and effectively has become an important issue in the world in recent years. Dye-sensitized solar cells (DSCs) have great potential to replace traditional Shixia solar cells due to their high photoelectric conversion efficiency, light weight and low manufacturing cost. The best energy conversion efficiency can be achieved by using an anthraquinone dye in dye-sensitized solar cells, such as N3- and N719 sensitized solar cells. Attempts to design and synthesize novel semi-symmetric sensitizers with higher device performance are in progress. There are two key factors affecting the performance of dye-sensitized solar cells, namely the strength of the metal-ligand charge transfer band (MLCT band) and the amount by which the dye can be loaded by the battery element. The metal sensitizing dye can be modified by 4 201223954 to extend or branch to the chromophore® square wire to modify the Wei group, thereby enhancing and expanding the metal _ ligand charge transfer band 'however, this method increases the volume of the dye molecule' The amount of dye that can be loaded onto the surface of the titanium dioxide is reduced. Therefore, the optimal length required for pure hair (4) becomes an interesting and important 4 questions, which can be fine-tuned to optimize the two opposite factors, thereby improving the performance of the component. SUMMARY OF THE INVENTION In order to solve the problem of the prior art, the present invention provides a photosensitizing dye, and the photoelectric conversion efficiency of the dye-sensitized solar cell using the dye can be improved. The present invention provides a compound of the formula (1) (IV).

Wherein, Xl is oxygen, sulfur or a code; X2 is hydrogen, alkyl, decyl, alkynyl, cyclohexyl, cycloalkenyl, hetero-weiyl, heterocyclic aryl or heteroaryl; m=M; Υΐ, Υ2 and Y3 are each independently selected from the group consisting of hydrogen, alkyl, dilute, alkynyl, secret, base, heterolyl, heterocycloalkenyl, aryl, heteroaryl, halogen, nitro, cyano , wind, _c〇〇Ra, 5 201223954 -0C(0)Ra, -C(0)NRbRc, and -NRbRc; the lanthanum is selected from A, yard, miscellaneous, silk, Weiji, a group consisting of a transyl group, a heterocyclic alkyl group, a heterocyclic group, a starting group, and a heterogeneous group; and Rc and each independently selected from the group consisting of a domain, a county, an alkenyl group, an alkynyl group, a ring-based group, and a ring-based group. , a heteroleptic group, a heterocyclic ring, a feed group, and (iv) a group of fragrant groups; or a nitrogen bond on a heterocyclic, heterocyclic or heteroaromatic group; and 2! and Z2 are independently selected Free hydrogen, deutero, dilute, block, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, heteroaryl, i, nitro, cyano, -0Rd, - C00Rd, 士0卿, 〇c(〇)Rd, -C(〇)NReRf,, -NReRf Group of; wherein & is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, heteroaryl and alkali metal ions a group consisting of <&>, alkynyl, cycloalkyl, cycloalkenyl, each independently selected from the group consisting of hydrogen, alkyl, dicycloheterocycloalkyl, cycloalkenyl, aryl and heteroaryl Group. The present invention also provides a titania electrode comprising the above staple compound. The present invention also provides a dye-sensitized solar cell comprising the above ruthenium compound. According to the above disclosure, the sensitizer dye of the present invention has two opposite factors (the intensity of the MLCT band and the adsorption loading on the surface of the titania) by a linear 2,2,-dithiophene group. Excellent, while exhibiting excellent photoelectric conversion efficiency (the compound of one of the inventions can be up to 9.5% in 201223954; 8.8% relative to the commercially available N3). This discovery is not only an optimization of the energy conversion efficiency of sensitizers containing light chromophores, but also represents an alternative strategy for improving dye sensitized solar cells. The drawings attached to the present invention can be used as a reference for describing specific embodiments and examples of the photosensitive dyes of the present invention. [Embodiment] The present invention provides a ruthenium complex represented by the following formula (I)

It: 'the lanthanide is oxygen, sulfur or selenium; χ2 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocyclic heteroaryl; alkyl, dilute, aromatic -〇C(0)Ra, selected from the group consisting of anthracenyl, heterocyclic 5 and each " suitable for Honda, alkynyl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkyl, heterocycloalkenyl Base, aromatic group or

a group consisting of a fluorenyl group, a aryl group, a aryl group, a heteroaryl group, a heterocycloalkenyl group or a heteroaryl group; a fluorenyl nucleus group, a heterocycloalkenyl group, or a group And a heterocycloalkyl group, 7 201223954 nitrogen bond; and zj z2 are each independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, _yl, hetero-wei, hetero-based hetero-C ( 0) a group consisting of NReRf, and -NReRf; wherein, a group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a heterocyclic ring, a π 'membered aromatic group, a fragrant base, and a metal ion structuring Group H is each independently selected from the group consisting of hydrogen, silk, alkenyl, alkynyl, cyclic, ^=heterocyclic, cycloalkenyl, and aromatic (tetra) groups. In a preferred embodiment, Zl and Ζ2 are each mono- or -P〇3HRd; wherein & is selected from hydrogen or metal ions. Then, in another preferred embodiment, the COORd is independently selected from the group consisting of

C00A, 〇 0 -C00A,

Plant or S C00A!; wherein Αι is selected from another preferred embodiment, the alkali metal ion transports ions. Ion or potassium ion. In the other preferred embodiments, the γ 1 Y2 and Y3 systems are each

Independently selected from hydrogen, CnH2n+1 or A2 = CpH2p+1, p = 1-15. In the best practice, the system is 钌 compound system 8 201223954

COOH

(JF-6), or COOH H〇〇c.

C8h" Η H The present invention also despise __ (JF_7). The nail-shaped complex. ', a titanium oxide electrode, which comprises the aforementioned two:: providing a dye-sensitized solar cell, It is obtained by using a reaction product and a solution (4) commercially available in a unique manner. 201223954 4 NMR spectroscopy is obtained by using a Bruker AMX 400 or AV400 spectrometer with tetramethyl zebra as an internal standard. Elemental analysis is performed by perkin_Eimer The 2400 CHN analyzer was used to measure the mass spectrum using a jmS-700 dual focus mass spectrometer (JEOL, TOKYO, JAPAN). The absorption spectrum was recorded by a uV-vis spectrometer (Jewlett-Packard 8453). The cyclic and square wave voltammetry systems were In a mercaptomethylamine solution (10_3M), a platinum plate was used as a working electrode, a platinum wire auxiliary electrode, and a silver/nitric acid reference electrode, which were obtained by an Instruments electrochemical analyzer. The auxiliary electrolyte was tetrafluoroborate tetra Butylammonium (〇·1 M)' and ferrocene was selected as the internal standard. The solution was deoxygenated with nitrogen for 10 minutes before measurement. The scanning speed of cyclic voltammetry was 100 mV s. Square wave voltammetry with potential 1 〇 m v increasing and measuring at a frequency of 25 Hz. The amount of adsorption loading of the dye on the titanium dioxide film must be determined by dissolving the titanium dioxide in a methanol solution of 氢氧化钠·M sodium hydroxide, and releasing the adsorbed dye. The UV-vis absorption spectrum is measured to quantify. The amount of each dye adsorbed is calculated by the different concentrations of each solution. The electrochemical impedance spectroscopy of the dye-sensitized solar cell is determined by the FRA2 module. The potential/constant current meter is obtained at a constant light emission intensity of 1 〇〇 mW/cm 2 and a frequency range of 10 mHz to 65 kHz. The bias voltage and the alternating current amplitude are respectively set to the open circuit voltage of the dye-sensitized solar cell and 10 mV. Synthesis of 5-octyl-(2·2-dithiophene)-5'-formaldehyde The synthesis of 5-octyl-(2,2-dithiophene)-5'-formaldehyde is carried out by the following method: Octyl-(2,2-monothiophene) (277.5 mg, 1. 〇mm〇l) was dissolved in a dry flask containing 30 mL of tetrahydrofuran under a nitrogen atmosphere. The solution was cooled in an ice bath with liquid nitrogen/acetone. Then add n-butyllithium (〇8, 128 mmol, 1.6 Μ n-hexane) dropwise After the ice bath was removed and the solution was warmed to room temperature, hydrazine-hydrazinopiperidine (1398 mg, 12 mm 〇1) was added. 201223954 After 6 hours, the solution was poured into 200 mL of cold water. The organic layer was separated, and the aqueous layer was extracted with diethyl ether and the organic layer was collected. After removing water from magnesium sulfate, the solvent was removed to obtain a crude product. The crude product was purified by column chromatography with chlorobenzene / hexane (1:1) The bright yellow liquid 5_octyl-(2,2-dithiophene-5'-furfural) of 239.1 mg (〇·78 mmol, yield 78_0 °/〇) was obtained. NMR (CDC13, 400 MHz) δ ppm: 9.86 (s, 1H), 7.69 (d, /= 4.0

Hz, 1H), 7.24 (d, /= 3.6 Hz, 1H), 7.22 (d, /= 4.0 Hz, 1H), 6.82 (d, J = 3.6 Hz, 1H), 2.82 (t, 2H), 1.68 ( m, 2H), 1.34 (m, 10H), 0.95 (t, 3H). EI-MS (m/z): 306.2 [M]+. 2-"5-octyl-(2,2'-dithiazide Synthesis of ha,-5,-yl-M gas-imidazole diterpenoid (obtip) 1,10-diazaphenanthrene-5,6-dione (254.3 mg, 1.2 mmol) and 5·octyl-(2 , 2'_diphenanthrene)-5'-wake (306.7 mg, 1.0 mmol), a mixture of acetic acid (1548.9 mg, 20.2 mmol) and glacial acetic acid (30 mL) was refluxed for 2 hours. Pour into 2 mL of cold water, and the resulting precipitate was separated by filtration. The crude product was washed with water and purified by column. The extract was dichloromethane/hexane/methanol (5:5:2). , obtaining a brown solid 2-[5-octyl-(2,2'-dithiophene)-5'-yl]·!hydrogen-imidazole [4,5-/|[1,1〇] phenanthroline ( 362.1 mg, 0.729 mmo, 73%), melting point 198 ° C. XH NMR ([D6] DMSO, 300 MHz) 5 ppm: 9.03 (d, / = 1.2 Hz, 2H), 8.83 (d, / = 7.8 Hz , 2H), 7.82 (m, 3H), 7.33 (d, / = 3.9 Hz, 1H), 7.26 (d, /= 3.6 Hz, 1H), 6.85 (d, / = 3.6 Hz, 1H), 2.79 (t , /= 7.4 Hz, 2H), 1.61 (m, 2H), 1.24 (m, 10H), 0.83 (t, / = ¢.5 jjz, 3H). EI-MS (m/z): 496.2 [M]+ · 11 201223954 iRufdcbDV) obtiD (NCSV> (JF-5), each of which is taken (p- isopropyl isopropyl) phenyl dicarbonate (306.3 mg, 0.5 mmol) and obtip (500.3 mg, 1.0 mmol) Anhydrous dimethylformamide (20 mL) was added. The reaction mixture was heated to 80 ° C and nitrogen was passed for 4 hours, then dcbpy (4,4'·dihydroxy acid-2,2'·bipyridine; 244.0 Mg, 1.0 mmol) The reaction mixture was refluxed at 160 ° C for 4 hours in the dark, then excess ammonium isothiocyanate was added to the reaction and heated to 13 Torr. (: Reaction for 5 hours. After the reaction, the solvent was removed by a cyclone concentrator, and the obtained product was collected and washed with water and diethyl ether. The obtained crude product was dissolved in decyl alcohol and passed through a column with methanol as a solvent. The main product was concentrated to give 335.3 mg (0.349 mmol, 35%) of EtOAc (m.p.). m, 2H), 8.93 (s, 1H), 8.71 (d, /= 8.1 Hz, 1H), 8.35 (m, 2H), 7.88 (d, /= 3.3 Hz, 1H), 7.83 (d, /= 4.8 Hz, 1H), 7.68 (d, /= 5.7 Hz, 1H), 7.59 (t, /= 6.5 Hz, 1H), 7.47 (d, / = 4.5 Hz, 1H), 7.34 (d, / = 3.6 Hz, 1H), 7.26 (d, /= 3.3 Hz, 1H), 6.85 (d, /= 3.3 Hz, 1H), 2.78 (t, 7= 7.2 Hz, 2H), 1.53 (t, /= 7.2 Hz, 2H) , 1.28 (m, 10H), 0.85 (t, /= 5.4 Hz, 3H). FAB-MS (w/z): 900.4 [M-NCS]' Ana丨· Calcd for C43H36N804RuS4: C 53.90, H 3.79, N 11.70, S 13.39. Found: C 53.72, H 3.86, N 11.49, S 12.98. Synthesis of 5-辜篡-f2.2',5,2"-dithiophene)

5-octyl-(2,2',5,2"-dithiophene) was synthesized in the following manner: 2,2',5,2"·dithiophene (247.6 mg' 1.0 mmol) in a dry flask Dissolved in 30 mL 12 201223954 tetrahydrofuran, protected with nitrogen during the process. The solution was cooled in a liquid nitrogen/acetone ice bath, then n-butyllithium (0.8 mL, 1.28 mmol, 1.6 hexanes) was added dropwise. The ice bath was then removed and the solution was warmed to room temperature and then 1 - ss. <RTIgt; After 6 hours, the solution was poured into 200 mL of cold water. Thereafter, the organic layer was separated, and the aqueous layer was extracted with diethyl ether and the organic layer was collected. After removing water from magnesium sulfate, the solvent was removed to obtain a granulated product. The crude product was purified by column chromatography eluting with hexane to afford 183 g (yield: 51%) (yield: 51%). H NMR (CDCI3, 400 MHz) δ ppm: 7.18 (d, J = 5.2 Hz, 1H), 7-13 (d, /= 3.2 Hz, 1H), 7.03 (d, /= 4.0 Hz, 1H), 6.97 (m, 3H), 6.66 (d, /= 3·2 Hz, 1H), 2.77 (t, /= 7.6 Hz, 2H), 1.66 (m, 2H), 1.27 (m, 10H), 0.86 (t, /= 6.8 Hz, 3H). FAB-MS (mfz): 360.1 [M]+. ^^--(2,2',5丄?''_Dithiophene^Formaldehyde Synthesis 5-octyl _(2,2,5,2 ·dithiophene) (36ΐ·3 mg, ! 〇mmol) was dissolved in a dry flask containing 30 mL of tetrahydrofuran under the protection of gas. The solution was ice bath in liquid nitrogen/acetone. After cooling, n-butyllithium (〇 8 mL, 1·28 mmol, 1.6 Μ n-hexane) was added dropwise, then the ice bath was removed and the solution was warmed to room temperature, and hydrazine was added. Pyridine (132 3 mg i 2 mmol). After 6 hours, the solution was poured into 2 mL of cold water. The organic layer was separated, and the aqueous layer was extracted with diethyl ether and the organic layer was collected. The solvent was removed to obtain the crude product. The succinated product was eluted with two w (1:1) to obtain a bright yellow solid of 285 5 1^ (= yield of 73%) 5- octyl _ (2, 2,, 5,,2,,_二嗔Phenyl)-5'-furfural, melting point 90. (: NMR (CDCI, 400 MHz) 5 ppm: 9.82 (s, 1H), 7.65 (d, /= 3.6 201223954

Hz, 1H), 7.26 (d, 7 = 4.0 Hz, 1H), 7.22 (d, J= 4.0 Hz, 1H), 7.05 (d, J = 1.2 Hz, 1H), 7.04 (d, J = 1.2 Hz, 1H), 6.71 (d, J = 3.6 Hz, 1H), 2.79 (t, /= 8.0 Hz, 2H), 1.67 (m, 2H), 1.24 (m, 10H), 0.88 (t, /= 6.8 Hz, 3H). FAB-MS (m/z): 389.1 [M+H]+. 1^5-octyl-(2,2,5,2"-dithiophene)_5,- some 1-1彘- oxazole "4.5-chuan 1,101 synthesis of phenidene (ottip) l,l〇_diazepine-5,6-dioxin (221.0 mg, 1.1 mmol) and 5-octyl_(2,2' ,5',2"-diphenanthene)_5'-曱路(388.3!11§,1〇111111〇1), a mixture of ammonium acetate (1553.2 mg '20·2 mmol) and glacial acetic acid (30 mL) After refluxing for 2 hours, the mixture was poured into 200 mL of cold water after the reaction, and the resulting precipitate was separated by filtration. The crude product was washed with water and purified by a column. The extract was di-methane/hexane/hexane. Alcohol (5:5:2), obtained as a brown solid 2-[5-octyl-(2,2',5',2''-dithiophene)-5,-yl]-1 hydrogen-isoxazole [4 , 5--|[1,10] phenanthroline (437.9 mg, 0.76 mmo, 76%), with a refining point of 223 °C. !H NMR ([D6]DMSO, 400 MHz) δ ppm: 9.04 (d, J = 3.6 Hz, 2H), 8.86 (s, 2H), 7.84 (m, 3H), 7.45 (d, /= 3.6 Hz, 1H), 7.40 (d, J = 3.6 Hz, 1H), 7.22 (d, /= 3.6 Hz, 1H), 7.17 (d, /= 3.2 Hz, 1H), 6.82 (d, J =3.2 Hz, 1H) , 2.78 (t, /= 7.6 Hz, 2H), 1.61 (m, 2H), 1.24 (m, 10H), 0.85 (t, 7 = 6.4 Hz, 3H). FAB-MS (m/z): 579.2 [ M]+. lEu(dcbpv)ottiDUNCShl (JF-6) was synthesized by adding (p-methylisopropyl)phenylphosphonium dichloride (306.5 mg, 0.5 mmol) and ottip (580.4 mg, 1.0 mmol) to anhydrous Mercaptocarboxamide (20 201223954 mL). The reaction mixture was heated to 80 ° C and nitrogen was bubbled through for 4 hours, after which 3 Torr was added. (4,4,_Dihydroxy acid-2,2'-bipyridine; 244.4 11^, 1.〇111111〇1). The reaction mixture was refluxed at 160 ° C for 4 hours in the dark, after which excess ammonium isothiocyanate was added to the reaction and heated to 130 ° C for 5 hours. After the reaction, the solvent was removed by a rotary concentrator, and the obtained product was collected and washed with water and diethyl ether. The crude product obtained was dissolved in methanol and passed through a column with methanol as a solvent. The main product was collected and concentrated to give 298.3 mg (0.29 mmo, 29%) of a white solid, melting point > 400 °C. *H NMR ([D6]DMSO, 400 MHz) δ ppm: 9.53 (m, 2H), 9.09 (m, 2H), 8.90 (s, 1H), 8.72 (d, /= 5.2 Hz, 1H), 8.35 ( m, 2H), 7.86 (d, / = 8.4 Hz, 1H), 7.83 (d, /= 5.4 Hz, 1H), 7.68 (d, /= 5.2 Hz, 1H), 7.60

(d, J = 4.8 Hz, 1H), 7.46 (m, 2H), 7.40 (d, J = 3.8 Hz, 1H), 7.20 (d, J = 3.8 Hz, 1H), 7.16 (d, J = 3.4 Hz , 1H), 6.81 (d, J = 3.4 Hz, 1H), 2.76 (t, /= 6.8 Hz, 2H), 1.58 (m, 2H), 1.25 (m, 10H), 0.84 (t, /= 6.8

Hz,3H). FAB-MS (zw/z): 1040.2 [M]+. Anal· Calcd for

C47H38N804RuS5: C 54.27, H 3.68, N 10.70, S 15.41. Found: C 54.67, H 4.06, N 10.83, S 15.11. 2,3-di-f5-octylc-phen-2-yl) , 3-di-(5-octyl嗔phen-2-yl)thiophene was synthesized in the following manner: 2,3-dibromothiophene (240.3 mg, 1.0 mmol) and trimethyl (5-octylthiophene-2_) The stannane (810.8 mg '2_3 mmol) is dissolved in 3 mL of anhydrous dimethylformamide, followed by bis(triphenylphosphine)palladium dichloride (35 5 mg, 〇〇61 mmol). As a catalyst. The mixture was refluxed for 22 hours under a nitrogen atmosphere, after which the solution was cooled to room temperature, and a 5% by weight concentration of vaporized money was added to terminate the reaction at 201223954 and the product was extracted with a gas-fired product. The organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate, distilled water and a saturated aqueous solution of sodium chloride. The obtained crude product was passed through a column with n-hexane as a solvent, and a bright yellow liquid 2,3_di-(5-octylthiophenyl) ° thiophene was obtained to obtain 353 4 mg (0.747 mmo, 75%). NMR (CDC13, 400 MHz) <5 ppm: 7.25 (<j, J = 5.2 Hz, 1H), 7.19 (d, /= 5.2 Hz, 1H), 7.02 (d, 3.6 Hz, 1H), 6.95 ( d, /= 3.6 Hz, 1H), 6.75 (d, /= 4.0 Hz, 1H>, 6.73 (d, /= 4 〇Hz Qiu 2 85 (8) 4H) 1.75 (m, 4H), 1.43 (m, 2GH) , G.97 (m, 6H) EI MS (4)): 472 3 [M]+. Synthesis of bis(5·octyl porphin-2-yl) porphin 2,3-di-(5-octyl)嗟 -2 -2 · · 噻 噻 ( 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 n-Butyl = 〇 · 8 ' L28 m_ ' h6 M is in the pit) added dropwise. The ice bath was then removed and the solution was warmed to room temperature, such as λν_methionine (14 〇 3 mg, L2 〇 1). After 6 hours, the night was poured into 2 〇〇 cold water, and the organic layer was separated, and the aqueous layer was extracted with diethyl ether and the organic layer was collected. After washing with water, the solvent was removed by removing water with anhydrous magnesium sulfate. Crude product. The crude product was purified by column column, and bright yellow (tetra) 2,3-mono-(5-octylthiophene) was obtained by pulverization of dimethyl sulphide/zhengyuan (ι: ι) to obtain mm 〇1 (yield 68%). -2-yl)thiophene)-5,-formaldehyde. 4 Xinjiang (OK: 丨3, tearing MHz) 5 ppm: 9 86 (sm) 7 % (sm) 7.10 (d, /= 3.6 Hz, 1H), 6.92 (d, /= 3.6 Hz, 1H), 6.74 ( d, /= 3.6 Hz, 201223954 1H), 6.71 (d, J = 3.6 Hz, 1H), 2.82 (m, 4H), 1.68 (m, 4H), 1.29 (m> 20H), 0.89 (m, 6H) EI-MS (m/z): 500.3 [M]+. 2_f2,3-dioctyl therapy phen-2-yl)- porphin _5-yl]-1 nitrogen-purine free 丨1.101 diazepine fdottip Synthesis of 1,10-diazaphenanthrene-5,6-dione (229.0 mg, 1.1 mmol) and 2,3-di-(5-octyl.cephen-2-yl). A mixture of thiophene-5'-amyl (510.3 mg, 1.0 mmol), ammonium acetate (1632.5 mg, 21.2 mmol) and glacial acetic acid (30 mL) was refluxed for 2 hours. After the reaction, the mixture was poured into 200. In the cold water of mL, the obtained precipitate was separated by filtration, and the crude product was washed with water and purified by a column. The extract was dichloromethane/hexane/methanol (5:5:2) to obtain a brown solid 2- [2,3-di-(5-octylthiophen-2-yl)-thiophen-5-yl]-1 hydrogen-mouth m-sit [4,5-/|[1,1〇] phenanthroline (456.3 mg, 0.66 mmol, 65%), mp 208 °C. ^ NMR ([D6]DMSO, 400 MHz) δ ppm: 9.01 (d, /= 3.2 Hz, 2Η), 8.85 (s, /= 8.4 Hz, 2H), 7.92 (s, 1H), 7.77 (dd, / = 3.2, 8.4 Hz, 2H), 7.09 (d, / = 3.6 Hz, 1H), 7.00 (d, /= 3.6 Hz, 1H), 6.79 (d, J= 3.2 Hz, 1H), 6.77 (d, J = 3.2 Hz, 1H), 2.77 (m, 4H), 1.62 (m, 4H), 1.27 (m, 20H), 0.86 (m, 6H). EI-MS (m/z): 690.4 [M]+. [Ruidcbpv)dottiDUNCSV>] i.TF-7) Synthesis of (p-decylisopropyl)phenylphosphonium dichloride (306.0 mg, 0.5 mmol) and dottip (692.8 mg, 1.0 mmol) Base amine (20 mL). The reaction mixture was heated to 80 ° C and nitrogen was bubbled over for 4 hrs, then dcbpy (4,4'-dihydroxy acid-2,2,-bipyridine; 244.9 mg, 1.0 mmol) was added. 201223954 The reaction mixture was refluxed at 160 ° C for 4 hours in the dark, after which excess ammonium isothiocyanate was added to the reaction and heated to 130. (Reaction: 5 hours. After the reaction, the solvent was removed by a cyclone concentrator, and the obtained product was collected and washed with water and diethyl ether. The obtained crude product was dissolved in decyl alcohol and passed through a column with decyl alcohol as a solvent. The main product was collected and concentrated to give 380.2 mg (0.329 mmo, 33%) of a black solid, melting point > 400 ° C. XH NMR ([D6] DMSO, 400 ΜΗζ) δ ppm: 9.57 (d, /= 6.0 Hz, 1Η), 9.53 (d, J = 4.8 Hz, 1H), 9.20 (s, 1H), 9.07 (s, J= 7.6 Hz, 1H), 8.98 (s, 1H), 8.72 (dd, J= 8.4 , 5.2 Hz, 1H), 8.39 (m, 2H), 7.99 (d, /= 5.2

Hz, 1H), 7.86 (d, /= 4.4 Hz, 1H), 7.75 (d, J= 4.8 Hz, 1H), 7.17 (d, J = 6.0 Hz, 1H), 7.09 (d, /= 5.2 Hz, 1H), 6.86 (m, 2H), 2.78 (m, 2H), 1.60 (m, 2H), 1.24 (m, 10H), 0.85 (t, /= 3.2 Hz, 3H). FAB-MS (m/z ):

1094.4 [M_NCS]+. Anal. €alcd for CS4H55N804RuSs: C 57.32, H 5.16, N 9.30, S 13.14. Found: C 56.88, H 5.16, N 9.30, S 13.14. The following flow chart is JF-5, JF- Synthesis pathway of 6 and JF-7

Wherein 'a represents a sub-ligand, ie 〇btip, ottip and dottip, dimethylformamide, 80 ° C, 4 hours; b represents dcbpy, dimethyl decylamine, 160 ° C ' 4 hours And c is representative of excess ammonium isothiocyanate, dimethylformamide, at 160 ° C for 5 hours. 18 201223954 Molecular model dyes JF-5, JF-6 and JF-7 geometry and electrochemical properties using density functional theory (DFT) and time-dependent density functional theory (time-dependent density functional theory) , TDDFT) to calculate the study, which is carried out by Gaussian 03 (G03) program, providing Becke's three-parameter hybrid function and Lee-Yang-Pap's gradient correction correlation function (Lee-Yang- Parr's gradient corrected correlation function, B3LYP) to the DFT method. The LanL2DZ effective nuclear energy is used for helium atoms, while the split-valence 6-31G** basis function is used for hydrogen, sulfur, carbon, oxygen and nitrogen atoms. The ground state geometry of the dye molecule is optimized for the gaseous state. The molecular orbital system is modeled using "〇&1^¥丨6 from 3.09", and the time-dependent density functional theory calculations of Khan-5, 讦-6 and 邛-7 are based on dimethylformamide as solvent. The class conductor polarization continuous model method (C-PCM) is obtained. The empirical solvent data, ie, the molecular radius and dielectric constant (ε)', were used in the C-PCM system at 2.647 A and 36.71, respectively. The 90 singlet excited states were determined by the geometrically optimal structures of JF_5, jF_6, and JF_7. GaussSuml.05 is used to analyze data for singlet excited state transitions. Preparation of Titanium Dioxide Electrode The preparation of the titanium carbide precursor and the formation of the electrodes were as follows. First, the titanium dioxide film as a photoanode is slowly dropped into the _ Μ = mixture according to the tetra(propyloxy) titanium. After the solution, the financial bath was heated to: and it was ashamed for 8 hours to reach the temple.胄 The resulting colloid is then subjected to high temperature to kill the secret ^Uc r2 201223954 hours to grow into titanium dioxide particles. After the gel is cooled to room temperature, it is oscillated by ultrasonic for ί. The titania colloid is then concentrated to a weight ratio of 13 to 3 ( (relative to the weight of titanium dioxide) in polyethylene glycol (pEG, Na: 2 = 00 i '(10)) 'polyethylene glycol system is used to prevent the film from drying during the drying process. Fragmentation. To form a titanium dioxide electrode, titanium isopropoxide (TTIP) and 2:methoxyethanol are used to form a metal organic solution. The metal organic solution was spin coated on a clean conductive <13Q/Square fluorine doped tin oxide glass' and then calcined at 500 °C for 30 minutes to form a tight titanium dioxide thin layer. A titanium dioxide paste was applied to the compact layer three times with a glass rod to obtain a suitable thickness. For the first coating, a titania colloid mixed with PEG having a molecular weight of 200,000 was used. For the second coating, a titanium dioxide paste containing a titania colloid and a molecular weight of 2 Å, ruthenium was used. The Paste 2 series is mixed with light-scattering particles of titanium dioxide (3 〇〇 nm, which is 30% by weight of the total oxidizer), and then used for the third (final) coating to reduce the light caused by backscattering. loss. The element f _ of the material-sensitized solar cell has a 0·4 X 0_4 cm 2 dioxygen oxide film electrode immersed in an acetonitrile/third butanol mixture containing 2 X 1 (Γ4 Μ dye sensitizer (volume ratio 1: 1). Take a platinum-finished FT〇 conductive glass with an activation area of 0.16 cm 2 as an auxiliary electrode, which is prepared by attaching a thickness of 60 μτη to the tape of polyg. The sensitized photoanode is acetonitrile. Wash and air dry. Fill the compartment with the electrolyte and place the photoanode above the auxiliary electrode' and then clamp it tightly to form the battery. The electrolyte consists of 0.6 丁基 butylmethylimidazolium (ΒΜΙΙ), 0.1 蛾 moth clock, 〇·〇5 Μ ΤΒΡ, 〇.03 Μ 峨, 〇5 Gu Bismuth sulphate (GuSCN) is dissolved in acetonitrile. The photoelectric characteristics of a solar cell with a mask (0_5 χ 〇5 cm2) utilizes 150 W of Peccell Solar simulation 20 201223954 (PEC-LU) is performed. The light intensity adjustment is transmitted through a neutral density filter set at the measurement position (battery), which is calibrated according to the reading of the radiant power meter (0riel, 70260). To i00niW/cm2. Photoionization of dye-sensitized solar cells The unique photocurrent-voltage curve is recorded using a constant potential/constant current meter (PGSTAT 30, Autolab, Eco-Chemie, The Netherlands). JF-5, JF-6 and · F-7 Ruthenium sensitizer [Ru(dcbpy)(〇btip)(NCS)2] ( JF-5, dcbpy =4,4'-dihydroxy acid-2,2,-bipyridine, obtip = 2-[5-xin -(2,2,-dithiophene)-5'-yl]-1 hydrogen-imidazole [4,5·/|[1,1〇]diazepine), [Ru(dcbpy)(ottip)-( NCS)2] (JF-6, ottip = 2-[5-octyl-(2,2,,5,,2,,-dithiophene)-5'-yl]-1 hydrogen-imidazole [4,5 -/|[1,1〇] phenanthroline), and [Ru(dcbpy)(dottip)(NCS)2] (JF-7, dottip = 2-[2,3-di-(5-octyl) The synthesis of thiophen-2-yl)-.cephen-5-yl]-1 hydrogen-mipropene [4,5-/|[1,1〇] phenanthroline) is a typical one-pot reaction. The uv-vis absorption spectra of this series of sensitizing compounds, jF_5, JF_6 and JF-7 in dimercaptoamine solution have three main characteristics, which are labeled as band I and band π in order of increasing energy. And the frequency band in (first picture and Table 1). The band Ι π is located at 310 nm, which overlaps with the τι-π transition of the inner ligand. The frequency band π is between 358 and 430 nm, and the sum contains π-π transitions and MLCT transitions. The molecular extinction coefficient of the lower energy MLCT band I at 520 nm in jp_6 is 149 x 1〇4M-icm-1, which is higher than JF-5 and JF-7. This enhancement is due to having a longer and planar oligothiophene backbone which not only increases the light harvesting capacity, but also maintains the non-localized structure throughout the molecule. Further, the frequency band U can be red-shifted and increased in value, presumably due to the extension of the length of the main chain of the porphyrin. Although it also has three thiophene groups, its branched and twisted thiophene groups destroy the linkage of the delocalized π-structure in d〇ttip (as shown in Figure 3). For this reason, JF-7 exhibits a lower MLCT intensity than the corresponding values of 21 201223954 at JF-5 and JF-6. Table 1 Optical Electrochemical Data and Battery Performance of JF-5, JF-6, and JF7 Dyes π-π·

KxlO^'crrT1] π-π* or 4d-7C*

Ej of Ru 1II/II 4ά-π* (V vs Fc/Fd Battery Performance' Ugly HOMO. (eV) Five LUM〇C (eV) (mA cm~2) y〇c (V)

JL "(% )e Γ' xlO_7i ol cm· JF-5 3.59(302)° 3.95(383) 1.26(520) 0.30 5I 3.66 18 3ί17 0Υ 0 73 0 71 os——Tr JF-6 3.83(299) 4.79(417) 1.49(520) 0.32 5.42 3.70 170,59( 071 07 «7 , JF-7 4.87(300) 2.75(.75) 1.05(520) 0.31 5.41 3.65 i3:lm:5 〇:7〇〇: 7〇54 05 Maximum absorption peak, Amax(nm). The A^Agl^〇3 reference electrode system is calibrated with erblocamine/ferrocene ion (Fc/Fc+) redox pair, and its electrochemical experiment is strict. The value of the acid 乂fJ,:: brewing amine 3 is ''Εηομο μ ugly' is calculated by the following equation: HOMO (e'SO-i^-iVj^ + S.ULUMCXeNO-fHOMo-i^A is based on dye The electron absorption error is used to estimate the ground state absorption energy. The battery performance data of djF_5, and JF-7 is the average of four measurements. * I乂N3•sensitized solar cells measured by the same component manufacturing program Let the photoelectric conversion efficiency of N3 be [Ru(dcbpy)2(NCS)2]) be 8.8%. The lanthanide is the dye concentration on the surface of the ruthenium dioxide film. The value of "bracket _ is integrated with jpeg and AM1.5G spectra. Calculation · Electrochemical properties of anthraquinone dyes JF-5, JF-6 and JF-7 Ring and square wave voltammetry were used to study (second and second maps), and their oxidation potentials are listed in Table 1. Cyclic voltammograms show that the oxidation and reduction potentials of all dyes are very close to each other. Further, square waves The oxidation potentials of JF-5, JF-6 and JF-7 in voltammograms are clearly shown as 〇.3〇, 0.32 and 0.31 (V vs Fc/Fc+), respectively. The highest occupied molecular orbital domain of all anthraquinone dyes ( The energy levels of hOMOs and the lowest unoccupied molecular domains (LUMOs) are calculated from the oxidation potential and the absorption edge obtained from the UV-vis absorption spectra (Tables 1 and 3). With titanium dioxide and redox electrolyte Comparing the energy levels of the conductive bands, these HOMO and LUMO energy levels are suitable for electron injection and dye regeneration. The optimal molecular structure of JF-5, JF-6 and JF-7 is like their calculated HOMOs and LUMOs energy levels. The frontier molecular orbital domain is revealed in the third graph. In the more microscopic examination, the frontier molecular domains of jF_5, jf-6 and JF-7 indicate that the HOMOs are located in the domain of Ru-t2g and NCS-π hybrids. This series of smear-stained LUMOs are evenly distributed to Ti 02 of 2,2'-bipyridyl-4,4,-dicarboxylic acid. The selection and calculation of the single-excited state transition of the MLCT band I of this series of enthalpy dyes with time-density functional theory 22 201223954 The results are shown in Table 2. Analysis of these transitions and orbital distributions indicates that band I of JF-6 contains a higher vibrational intensity than JF-5 (/=〇11711; 66%) and JF-7 (/=0.1152; 57%). (/=0.1625) and the possibility of a higher MLCT transition (72%). This result again indicates that the sensitizer having a longer and planar oligophene group has the ability to enhance the strength of the MLCT. The experimental and predicted electrical spectra are generally positively supported. Table 2, JF-5, JF-6 and JF-7 in dimercaptoamine, respectively, in the ViLCT band I, the density functional theory of singlet excited state transition selection results 0.0239 0.0006 0.1171 0.0034 0.0237 0.0006 0.0003 0.1625 0.0233 0.0006 0.1152 0.0005 Dye wavelength (nm) ^5 672.8 595.9 548.6 523.8 JF-6 672.3 597.2 564.2 548.1 Scare _7 671.1 594.4 547.4 514.2 Main distribution HOMO-^LUMO (79%) HOMO-3-LUMO (67%) HOMO -2—LUMO (66%) HOMO-1—LUMO (73%) HOMO-1-^LUMO (86%) HOMO-2—LUMO (71%) HOMO—LUMO (79%) HOMO-3-^LUMO ( 72%) HOMO-LUMO (853⁄4) HOMO-3-LUMO (58%) HOMO-2-LUMO (57%) HOMO-1-LUMO (80%) The fourth figure shows JF_5, JF-6 and JF-7 The current photon-to-cuirent conversion efficiency (IPCE) curve of the solar cell. The JF-5 sensitized solar cell exhibits a short-circuit photocurrent density (jsc) of 18.3 mAcn T2 and an open circuit voltage of 0 73 (u and 〇·71 fill factor (fill fact〇r, f ) ' corresponding to the standard am 1 5 The solar illuminance conditions showed a high photoelectric conversion efficiency of 9.5% (component data are listed in Table 1), while the efficiency of 叮-6 and 邛-7 was 8.7% and 6.4%, respectively. By 1?(:£ with standard AM 1.5 sun The total short-circuit photocurrent density calculated by the overlap of the emission spectra ("4;) is 17.0 mA cm-2, and the mismatch factor of the calculated photocurrent density is less than 1.08. By IPcEj% 23 201223954 The short-circuit photocurrent density (Jsc) series of all dyes obtained from the overlap of standard AM 1.5 solar emission spectra is shown in Table 1. In addition, compared to JF-6 (84%) and JF-7 (76%), JF-5 The IPCE curve (as shown in Figure 4) is over 80% in the 400-600 nm range and 92% highest at 523 nm. The measurement of dye adsorption (listed in Table 1) indicates that compared to JF- 6 (1.1 X 10-7 molcm-2) and JF-7 (0.5 X l (T7molcnT2), JF-5 has a higher dye adsorption capacity on the surface of titanium dioxide 1.8 X 1 (T7 mol cm—2). The fifth graph shows the relationship between ε, Γ and β of the JF-5, JF-6 and JF-7 MLCT bands I. Although JF-5 only shows the second highest The MLCT intensity, but the photoelectric conversion efficiency curve shows that JF-5 containing oligothiophene group (2,2,-dithiophene) can obtain the best overall effect, resulting in the highest conversion efficiency. Electrochemical impedance spectra (Electrochemical impedance spectra ' EIS) pointed out that these dye-sensitized solar cells contain three main resistors corresponding to three half-turns, respectively, from the first to the third, respectively, the resistance of the auxiliary electrode charge transfer, the dye-absorbing titanium dioxide / electrolyte interface The resistance common to the electron transfer of the titanium dioxide nanostructure and the diffusion of the triiodide ions to the electrolyte. The sixth figure clearly shows that the second half circle is sequentially increased by JF-5 < JF-6 < JF-7. Phenomenon shows that the overall resistance of the titanium dioxide/electrolyte interface of JF-5 sensitized solar cell to the electron transfer of titanium dioxide nanostructure is smaller than that of JF-6 and JF-7 sensitized solar cells. The photoelectricity of the length of oligothiophene group is changed by changing light. Conversion efficiency May be of good absorption UV-vis spectroscopy, electrochemical data, measure the amount of adsorbed dye, electrochemical impedance spectroscopy, explained DFT (density functional theory, DFT) and time-dependent density functional theory. In summary, we have provided the design and synthesis of novel sensitizers with excellent photoelectric conversion efficiency, and optimized the light-recovering oligophene group containing 2,2,-dithiophene to make it excellent. Component performance. This finding not only allows the photoelectric conversion efficiency of the sensitizing compound containing the oligothiophene group to be optimized, but also indicates the possible molecular design of the dye-sensitized solar cell. Other Embodiments All of the features disclosed in this specification may be combined with other methods, and each of the features disclosed in this specification may be selectively replaced with the same, equal or similar purpose features, and thus, in particular, In addition to the features, all of the features disclosed in this specification are only one of the equivalent or similar features. While the invention has been described above in terms of the preferred embodiments thereof, it is not intended to limit the invention, and various modifications and changes can be made without departing from the spirit and scope of the invention. 25

Claims (1)

201223954 VII. Patent application scope: 1. A bismuth complex represented by the following formula (I) Wherein 'X! is oxygen, sulfur or sillica; ring-based, cycloaliphatic, heterocyclic X2 is hydrogen, alkyl, alkenyl, alkynyl, arduous ^ yard base, heterocyclic base, aromatic Or heteroaryl; m = 1 -4 ; each independently selected from hydrogen, silk, fluorenyl, aryl, fluorenyl, heterocyclic, aryl, heteroaryl, halogen, nitro, luxuriant , squash, sulphate, alkynyl, cyclosporin, T#冰# Α heterocyclenyl, aryl and heteroaromatic di-, heterocycloalkyl, alkenyl, hetero-wei, hetero-yl , aryl = j, the ring, or the nitrogen bond of the heterocyclic group, the heterocyclic group, and the heterocyclic group, and the oxime 2 are independently selected from the group consisting of hydrogen, an alkyl group, a rare group f, Terpene, heterocycloalkyl, heterocycloalkyl]: arylalkane, nitro, cyano, heteroaryl, -qcONReRf, _NReRf constitute 3: 〇C(0)Rd, 砰, ·, The middle Rd is selected from the group consisting of hydrogen, 26 201223954 alkyl, alkynyl, alkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocyclic aryl, aryl, and metal ions.丨 and Re and the department are independent The group is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, cycloalkenyl, aryl and heteroaryl. 2. For example, the above-mentioned Z and selected from ^Rd; wherein the patent is the scope of the patent application! The staple complex described in the item, wherein each of the lines is independently selected from 2 4. If the scope of the patent application 帛 or +, '134^ 帛1, the above-mentioned 2 and Υ3 series are independently selected from hydrogen, CnH2n+i or -A2 27 201223954 COOH 7. The bismuth complex as described in claim 1 of the patent application is 8. The ruthenium complex according to item 1 of the patent application, which is (JF-6) 〇 COOH A titania electrode comprising the ruthenium complex described in claim 1 of the patent application. 10. A dye-sensitized solar cell comprising the ruthenium complex as described in claim 1 of the scope of the patent application. 28