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Bichromic bipodal triphenylamine-based dyes with high photo-electron conversion at low light intensities

10978255 · 2021-04-13

    Inventors

    Cpc classification

    International classification

    Abstract

    A bichromic bipodal triphenyl amine based dye of the following formula: ##STR00001## TABLE-US-00001 n 0 1 0 2 2 2 0 1 3 3 3 3 0 1 2 m 0 0 1 0 1 2 2 2 0 1 2 3 3 3 3 ##STR00002## Wherein R= ##STR00003##

    Claims

    1. A bichromic bipodal triphenylamine-based dye selected from the group consisting of: ##STR00026## wherein Donor (D) is a triphenylamine that is coupled through a p-spacer to an acceptor (A) capable of anchoring strongly to a semiconductor; wherein Anchor (A) is selected from acceptor/anchoring groups comprising electron-withdrawing carboxylic acid derivatives, conjugated to the p-spacer; and wherein p-spacer is selected from a p-conjugated spacer.

    2. A bichromic bipodal triphenyl amine based dye of formula: ##STR00027## TABLE-US-00006 n 0 1 0 2 2 2 0 1 3 3 3 3 0 1 2 m 0 0 1 0 1 2 2 2 0 1 2 3 3 3 3 Wherein R is selected from O—CH.sub.3 ##STR00028##

    3. A process to synthesize a bichromic bipodal triphenylamine based dye wherein R is defined in claim 2, said process comprising: ##STR00029## ##STR00030##

    4. A process to synthesize bichromic bipodal triphenylamine based dye wherein R is defined in claim 2, said process comprising: ##STR00031## ##STR00032## ##STR00033## ##STR00034##

    5. The process of claim 3 wherein I) is N-bromosuccinimide (1.10 eq), THF-EtOAc (1:1), 2 days; II) Pd(PPh.sub.3).sub.4 (0.10 eq), NaOH (8 eq), THF:water (9:1), reflux 12 hours; III) cyanoacetic acid (4 eq), piperidine (0.25 eq), CHCb, reflux 8 hours; IV) acetic acid: water (2:1), reflux 12 hours; V) 1) n-BuLi (1.2 eq) dropwise, −78° C. dry THF 2) −78° C. 15 min 3) boronic ester (2 eq) one portion, −78° C. 4) MeOH quench; VI) Ethylene glycol (3 mL), p-TsOH (0.2 eq), toluene (50 mL), Dean-Stark, reflux overnight.

    6. The process of claim 4 wherein I) is N-bromosuccinimide (1.10 eq), THF-EtOAc (1:1), 2 days; II) Pd(PPh.sub.3).sub.4 (0.10 eq), NaOH (8 eq), THF:water (9:1), reflux 12 hours; III) cyanoacetic acid (4 eq), piperidine (0.25 eq), CHCb, reflux 8 hours; IV) acetic acid:water (2:1), reflux 12 hours; V) 1) n-BuLi (1.2 eq) dropwise, −78° C. dry THF 2) −78° C. 15 min 3) boronic ester (2 eq) one portion, −78° C. 4) MeOH quench; VI) Ethylene glycol (3 mL), p-TsOH (0.2 eq), toluene (50 mL), Dean-Stark, reflux overnight.

    7. A dye-sensitized solar cell (DSSC) device comprising a dye of claim 1 wherein said dye is sensitized at diffuse light levels lower than about 100 mWcm.sup.−2.

    8. A dye-sensitized solar cell (DSSC) device comprising a dye of claim 2 wherein said dye is sensitized at diffuse light levels lower than about 100 mWcm.sup.−2.

    9. A dye-sensitized solar cell (DSSC) device comprising a dye of claim 1 wherein said dye is sensitized at diffuse light levels at about 25 mWcm.sup.−2 to 5 mWcm.sup.−2.

    10. A dye-sensitized solar cell (DSSC) device comprising a dye of claim 2 wherein said dye is sensitized at diffuse light levels at about 25 mWcm.sup.−2 to 5 mWcm.sup.−2.

    11. A dye-sensitized solar cell (DSSC) device comprising a dye of claim 1 wherein said dye is sensitized at diffuse light levels over than from about 10 mWcm.sup.−2.

    12. A dye-sensitized solar cell (DSSC) device comprising a dye of claim 2 wherein said dye is sensitized at diffuse light levels over than from about 10 mWcm.sup.−2.

    13. A Dye-sensitized solar cell (DSSC) device compromising at least one of the dyes of claim 1.

    14. A Dye-sensitized solar cell (DSSC) device compromising the dyes of claim 2.

    15. A dye-sensitized solar cell (DSSC) device comprising at least one of dye 4, 9, 13, 18 and combinations thereof.

    16. The device of claim 14 wherein said dye is 4a.

    17. The device of claim 14 wherein said dye is 9a.

    18. The device of claim 14 wherein said dye is 13a.

    19. The device of claim 14 wherein said dye is 18a.

    20. The compound of claim 2 wherein said compound is ##STR00035## wherein R═OCH.sub.3.

    21. The compound of claim 2 wherein said compound is ##STR00036##

    22. The compound of claim 2 wherein said compound is ##STR00037##

    23. The compound of claim 2 wherein said compound is ##STR00038##

    24. The DSSC device of claim 14, wherein said DSSC device functions at diffuse light levels lower than about 100 mWcm.sup.−2.

    25. The DSSC device of claim 14, wherein said DSSC device functions at diffuse light levels at about 25 mWcm.sup.−2 to 5 mWcm.sup.−2.

    26. The DSSC device of claim 14, wherein said DSSC device functions at diffuse light levels over than from about 10 mWcm.sup.−2.

    Description

    BRIEF DESCRIPTION OF THE FIGURES

    (1) FIG. 1 provides a plot of wavelength versus extinction of coefficient of several dyes described herein.

    (2) FIG. 2 provides a plot of light intensity versus % efficiency of several dyes described herein at different light levels.

    (3) FIG. 3 provides a plot of light intensity versus efficiency of several dyes described herein with deoxycholic acid at different light levels.

    DETAILED DESCRIPTION

    (4) The following provides examples of the bichromic bipodal triphenylamine dyes described herein.

    (5) Synthesis of Compound 2:

    (6) ##STR00014##

    (7) Under an atmosphere of N.sub.2, diformylTPA (2.83 g, 9.41 mmol) was dissolved in 75 mL of THF:EtOAc (1:1) and N-bromosuccinimide (1.84 g, 10.4 mmol) was added in one portion. The flask was covered with Al foil and the mixture was stirred overnight. Volatiles were removed in vacuo and the crude was purified via column chromatography over silica using hexanes:EtOAc (3:2) as the eluent, affording the desired product as a yellow-green solid (2.33 g, 65%). 1H NMR (400 MHz, chloroform-d3): δ=9.91 (a, s, 2H), 7.79 (b, d, 4H, 3JHH=8 Hz), 7.50 (d, d, 2H, 3JHH=8 Hz), 7.18 (c, d, 4H, 3JHH=8 Hz), 7.05 (e, d, 2H, 3JHH=8 Hz).

    (8) Synthesis of Compound 3a:

    (9) ##STR00015##

    (10) Under an atmosphere of N.sub.2, compound 2 (0.282 g, 0.74 mmol) was dissolved in 60 mL of THF:H.sub.2O (9:1) and compound B (0.42 g, 0.97 mmol) was added into the same flask. The flask was sparged for 15 minutes. The flask was charged with Pd(PPh.sub.3).sub.4 (10 mol %) followed by NaOH (8 eq) and refluxed at the solvents boiling point overnight. Volatiles were removed in vacuo and an extraction with DCM was performed. The crude was purified via column chromatography over silica using using a gradient elution from DCM to hexanes:EtOAc (3:2) affording the desired product as a yellow solid (0.251 g, 47%). 1H NMR (400 MHz, chloroform-d3): δ=9.90 (a, s, 2H), 7.79 (b, d, 4H, 3JHH=8 Hz), 7.56 (e, d, 2H, 3JHH=8 Hz), 7.40 (f, d, 2H, 3JHH=8 Hz), 7.23 (c, d, 4H, 3JHH=8 Hz), 7.18 (d, 2H, 3JHH=8 Hz), 7.09 (h, d, 4H, 3JHH=8 Hz), 6.98 (g, 2H, 3JHH=8 Hz), 6.85 (i, d, 4H, 3JHH=8 Hz), 3.81 (j, s, 6H).

    (11) Synthesis of Compound 4a:

    (12) ##STR00016##

    (13) Compound 3a (0.233 g, 0.38 mmol) was dissolved in a minimal amount of CHCl.sub.3 and cyanoacetic acid. 2 drops of piperidine was then added. The mixture was refluxed at the solvents boiling point overnight. The organic layer was washed with HCl 1 N and volatiles removed in vacuo, in one alternative at a pressure of 30 mbar. The crude was recrystallized in DCM:hexane (1:1) as a crimson red solid (0.091 g, 39%); IR (cm−1) 2229, 1720. 1H NMR (400 MHz, dimethylsulfoxide-d6): δ 8.21 (a, s, 2H), 8.01 (b, d, 4H, 3JHH=8 Hz), 7.66 (e, d, 2H, 3JHH=8 Hz), 7.51 (f, d, 2H, 3JHH=8 Hz), 7.22 (d, d, 2H, 3JHH=8 Hz), 7.19 (c, d, 4H, 3JHH=8 Hz), 7.05 (i, d, 4H), 6.92 (h, d, 4H, 3JHH=8 Hz), 6.81 (g, d, 2H, 3JHH=8 Hz) 3.75 (s, 6H). 13C{1H} NMR (100 MHz, dimethylsulfoxide-d6) δ=163.70, 155.93, 152.99, 149.92, 148.05, 143.05, 139.83, 137.88, 132.73, 130.37, 127.61, 127.24, 126.95, 125.99, 122.60, 119.09, 116.63, 115.01, 55.25. HRMS (ESI): m/z 737.24194 ((M−H]−) calculated for C.sub.46H.sub.34N.sub.4O.sub.6: m/z 737.24056.

    (14) Synthesis of Compound 6:

    (15) ##STR00017##

    (16) Under an atmosphere of N.sub.2, compound A (2.00 g, 5.26 mmol) was dissolved in 60 mL of THF:H.sub.2O (9:1) and compound 2 (1.105 g, 5.26 mmol) was added into the same flask. The flask was sparged for 15 minutes and then charged with Pd(PPh.sub.3).sub.4 (10 mol %) followed by NaOH (8 eq) and refluxed at the solvents boiling point overnight. Volatiles were removed in vacuo, in one alternative at 30 mbar, and an extraction with DCM was performed. The crude was purified via column chromatography over silica using hexanes:EtOAc (3:2) affording the desired product as a neon yellow, waxy oil. (1.0381 g, 51%). 1H NMR (400 MHz, chloroform-d3): δ=9.91 (a, s, 2H), 7.79 (b, d, 4H, 3JHH=8 Hz), 7.62 (e, d, 2H, 3JHH=8 Hz), 7.31 (d, d, 2H, 3JHH=8 Hz), 7.22 (c, 4H, 3JHH=8 Hz), 7.17 (f+h, d, 2H, 3JHH=8 Hz), 7.10 (g, t, 1H, 3JHH=8 Hz).

    (17) Synthesis of Compound 7:

    (18) ##STR00018##

    (19) Under an atmosphere of N.sub.2, compound 6 (0.30 g, 0.79 mmol) was dissolved in 75 mL of THF:EtOAc (1:1) and N-bromosuccinimide (0.16 g, 0.9 mmol) was added in one portion in a flask. The flask was covered with Al foil and the mixture was stirred at roughly 300 rpm with a magnetic stir plate at room temperature overnight. Volatiles were removed in vacuo, in one alternative at 30 mbar, and the crude was purified via column chromatography over silica using hexanes:EtOAc (3:1) as the eluent, affording the desired product as a yellow waxy solid. (0.201 g, 57%). 1H NMR (400 MHz, chloroform-d3): δ=9.91 (a, s, 2H), 7.79 (b, d, 4H, 3JHH=8 Hz), 7.51 (d, d, 2H, 3JHH=8 Hz), 7.22 (c, d, 4H, 3JHH=8 Hz), 7.16 (e, d, 2H, 3JHH=8 Hz), 7.04 (f+g, s, 2H).

    (20) Synthesis of Compound 8a:

    (21) ##STR00019##

    (22) Under an atmosphere of N.sub.2, compound 7 (0.622 g, 1.34 mmol) was dissolved in 60 mL of THF:H.sub.2O (9:1) and compound B (0.638 g, 1.48 mmol) was added into the same flask. The flask was sparged for 15 minutes. The flask was charged with Pd(PPh.sub.3).sub.4 (10 mol %) followed by NaOH (8 eq) and refluxed at the solvents boiling point overnight. Volatiles were removed in vacuo, in one alternative at 30 mbar, and an extraction with DCM was performed. The crude was purified via column chromatography over silica using hexanes:EtOAc (3:1) affording the desired product as a yellow solid. (0.361 g, 39%). 1H NMR (400 MHz, chloroform-d3): δ=9.90 (a, s, 2H), 7.79 (b, d, 4H, 3JHH=8 Hz), 7.61 (f+g, d, 2H, 3JHH=8 Hz), 7.43 (d, d, 2H, 3JHH=8 Hz), 7.23 (c, d, 4H, 3JHH=8 Hz), 7.16 (h+e, d, 4H, 3JHH=8 Hz), 7.08 (k, d, 4H), 6.92 (i, d, 2H, 3JHH=8 Hz), 6.85 (j, d, 4H, 3JHH=8 Hz), 3.81 (s, 6H). 13C{1H} NMR (100 MHz, CDCl3) δ 190.62, 156.21, 151.91, 148.58, 144.58, 144.42, 140.88, 140.67, 132.52, 131.59, 131.49, 127.24, 126.86, 126.40, 126.20, 124.42, 123.08, 122.80, 120.50, 114.89, 55.63.

    (23) Synthesis of 9a:

    (24) ##STR00020##

    (25) Compound 8a (0.434 g, 0.632 mmol) was dissolved in a minimal amount of CHCl.sub.3 and cyanoacetic acid. 2 drops of piperidine was then added. The mixture was refluxed at the solvents boiling point overnight. The organic layer was washed with HCl 1 N and volatiles removed in vacuo. The crude was recrystallized in DCM:hexane (1:1) as a crimson red solid (0.217 g, 50%). IR (cm−1) 2223.819, 1695.602. 1H NMR (400 MHz, dimethylsulfoxide-d6): δ=8.22 (a, s, 2H), 8.01 (b, d, 4H, 3JHH=8 Hz), 7.70 (e, d, 2H, 3JHH=8 Hz), 7.47 (h+g, m, 3H), 7.32 (fid, 1H, 3JHH=8 Hz), 7.19 (c+d, m, 6H), 7.03 (k, d, 4H, 3JHH=8 Hz), 6.91 (j, d, 4H, 3JHH=8 Hz), 6.77 (I, d, 2H, 3JHH=8 Hz), 3.74 (l, s, 6H). 13C{1H} NMR (100 MHz, CDCl3) δ 163.67, 155.93, 152.98, 149.75, 148.08, 143.67, 143.28, 140.05, 139.69, 132.72, 131.53, 127.21, 126.82, 126.67, 126.15, 126.10, 125.09, 123.30, 122.79, 119.23, 116.56, 114.99, 100.70, 55.23, 30.65. HRMS (ESI): m/z 819.22961 ((M−H]−) calculated for C.sub.50H.sub.36N.sub.4O.sub.6S: m/z 819.22828.

    (26) Synthesis of Compound 11a:

    (27) ##STR00021##

    (28) Under an atmosphere of N.sub.2, para-tribromo-triphenylamne (1.5 g, 3.11 mmol) was dissolved in 150 mL of THF:H.sub.2O (9:1) and compound B (1.475 g, 3.42 mmol) was added into the same flask. The flask was sparged for 15 minutes. The flask was charged with Pd(PPh.sub.3).sub.4 (10 mol %) followed by NaOH (8 eq) and refluxed at the solvents boiling point overnight. Volatiles were removed in vacuo and an extraction with DCM was performed. The crude was purified via column chromatography over silica using hexanes:EtOAc (7:3) affording the desired product as a white solid. (0.410 g, 19%). 1H NMR (400 MHz, chloroform-d3): δ=7.44 (d, d, 2H, 3JHH=8 Hz), 7.39-7.33 (a+d, m, 6H), 7.08 (b+c, d, 6H, 3JHH=8 Hz), 6.97 (h, d, 4H, 3JHH=8 Hz), 6.84 (f+g, d, 6H, 3JHH=8 Hz), 3.80 (l, s, 6H). HRMS (ESI): m/z 706.0657 calculated for C.sub.48H.sub.36N.sub.2O.sub.4S.sub.2: m/z 706.07.

    (29) Synthesis of Compound 12a:

    (30) ##STR00022##

    (31) Under an atmosphere of N.sub.2, compound 11a (0.410 g, 0.58 mmol) was dissolved in 60 mL of THF:H.sub.2O (9:1) and compound C (0.344 g, 1.22 mmol) was added into the same flask. The flask was sparged for 15 minutes. The flask was charged with Pd(PPh.sub.3).sub.4 (10 mol %) followed by NaOH (8 eq) and refluxed at the solvents boiling point overnight. Volatiles were removed in vacuo and an extraction with DCM was performed. The crude was purified via column chromatography over silica using hexanes:EtOAc (7:3) affording the desired product as a red solid. (0.023 g, 5%). 1H NMR (400 MHz, chloroform-d3): δ=9.87 (a, s, 2H), 7.72 (b, d, 2H, 3JHH=8 Hz), 7.58 (d, d, 4H, 3JHH=8 Hz), 7.51 (c, d, 2H, 3JHH=8 Hz), 7.40 (g, d, 2H, 3JHH=8 Hz), 7.34 (h, d, 2H, 3JHH=8 Hz), 7.18 (e+f, m, 6H, 3JHH=8 Hz), 7.09 (j, d, 4H, 3JHH=8 Hz), 6.99 (i, d, 2H, 3JHH=8 Hz), 6.85 (k, d, 4H, 3JHH=8 Hz), 3.81 (l, s, 6H). HRMS (ESI): m/z 768.211110 calculated for C.sub.48H.sub.36N.sub.2O.sub.4S.sub.2: m/z 768.21.

    (32) Synthesis of Compound 13a:

    (33) ##STR00023##

    (34) Compound 12a (0.027 g, 0.03 mmol) was dissolved in a minimal amount of CHCl.sub.3 and cyanoacetic acid. Piperidine was then added. The mixture was refluxed at the solvents boiling point and monitored via thin layer chromatography. The organic layer was washed with HCl 1 N and volatiles removed in vacuo. The crude was recrystallized in DCM:hexane (1:1) as a crimson red solid (0.023 g, 84%). IR (cm−1) 2222.788, 1649.201. 1H NMR (400 MHz, dimethylsulfoxide-d6): δ=8.44 (a, s, 2), 8.00 (b, m, 2H), 7.81 (d, d, 4H, 3JHH=8 Hz), 7.67 (e, d, 4H, 3JHH=8 Hz), 7.54 (c, d, 2H, 3JHH=8 Hz), 7.30-7.23 (g+h, m, 6H, 3JHH=8 Hz), 7.10 (k, d, 4H, 3JHH=8 Hz), 6.93 (j+i, d, 6H, 3JHH=8 Hz), 3.80 (l, s, 6H). 13C{1H} NMR (100 MHz, dimethylsulfoxide-d6) δ 200.01, 155.86, 147.16, 147.16, 144.51, 144.51, 139.98, 135.90, 135.90, 135.13, 135.13, 130.85, 130.85, 129.30, 127.26, 127.03, 126.80, 125.44, 125.43, 123.95, 123.73, 119.46, 118.80, 115.02, 55.29, 43.68, 30.71, 22.20, 21.72.

    (35) Synthesis of Compound 5:

    (36) ##STR00024##

    (37) DiformylTPA (0.950 g, 3.15 mmol) was dissolved in a minimal amount of CHCl.sub.3 and cyanoacetic acid. 2 drops of piperidine was then added. The mixture was refluxed at the solvents boiling point and monitored via thin layer chromatography. The organic layer was washed with HCl 1 N and volatiles removed in vacuo. The crude was recrystallized in DCM:hexane (1:1) as a dark orange solid (0.026 g, 0.019%). IR (cm−1) 2217.502, 1699.994. 1H NMR (400 MHz, dimethylsulfoxide-d6): δ=8.22 (a, s, 2), 8.01 (b, d, 2H, 3JHH=8 Hz), 7.48 (e, t, 2H, 3JHH=8 Hz), 7.33 (f, t, 1H, 3JHH=8 Hz), 7.23 (d, d, 2H, 3JHH=8 Hz), 7.16 (c, d, 4H, 3JHH=8 Hz). 13C{1H} NMR (100 MHz, dimethylsulfoxide-d6) δ 163.95, 154.21, 152.60, 150.28, 133.76, 132.19, 132.15, 129.22, 126.18, 126.10, 123.50, 123.45, 121.89, 121.84, 116.94, 116.80, 100.75.

    (38) Based on the tables below, it is observed that the present dye in DSSC has 1) increased panchromatic absorption into the near-IR as observed in the UV-Vis spectra displayed below; 2) improved redox stability and dye lifetime as a result of the incorporation of two redox robust donor units; and 3) improved electronic communication between interfaces as a result of the bipodal structure of the dye relative to the previously published benchmark dye L1 pictured below (Hagberg, D. P.; Marinado, T.; Karlsson, K. M.; Nonomura, K.; Qin, P.; Boschloo, G.; Brinck, T.; Hagfeldt, A.; Sun, L. J. Org. Chem. 2007, 72 (25), 9550-9556).

    (39) ##STR00025##
    Referring now to FIG. 1, there is shown an Ultraviolet visible (UV-Vis) spectra of dyes L1, 5, 13a, 9a and 4a collected in dichloromethane (DCM).

    (40) Referring now to FIG. 2, there is shown efficiencies of dyes L1, 4a, 9a and 13a at high and low light intensities and the percent change in efficiency. This is tabulated below.

    (41) TABLE-US-00003 Efficiency at 73 Efficiency at Change from High Dye mW/cm.sup.2 (%) 5 mW/cm.sup.2 (%) to Low Light (%) L1 1.7 ± 0.80 0.8 ± 0.42 103 4a 1.33 5.69 367 9a 1.7 ± 0.28 3.7 ± 0.65 250 13a  2.1 ± 0.18 3.0 ± 0.41 199

    (42) Note that all tests were carried out in triplicate at a minimum except when standard deviation is not reported, in which case testing was carried out in duplicate.

    (43) Referring now to FIG. 3 there is shown efficiencies of dyes 4a, 9a and 13a with added deoxycholic acid at high and low light intensities and the percent change in efficiency. The results are tabulated below.

    (44) TABLE-US-00004 Efficiency at 73 Efficiency at Change from High Dye mW/cm.sup.2 (%) 5 mW/cm.sup.2 (%) to Low Light (%) 4a 1.7 ± 0.84 4.4 ± 0.88 380 9a 1.80 4.31 392 13a  2.0 ± 0.57 2.3 ± 0.75 143

    (45) In the table below, open circuit voltage (V.sub.oc) is defined as the point where current drops to zero, short circuit current (J.sub.sc) is defined as the maximum current generated, fill factor (FF) is a measure of the squareness of the curve, and the incident power (P.sub.in) is the power of the light used to test the solar cell. These values are used to determine efficiency from the following relationship,

    (46) η = V oc × J sc × FF P i ⁢ ⁢ n
    in which V.sub.oc is measured in volts (V), J.sub.sc is measured in milliamperes per centimeter squared (mA/cm.sup.2), FF is unit less, and P.sub.in is measured in milliwatts per centimeter squared (mW/cm.sup.2).

    (47) TABLE-US-00005 Average Voc Jsc Pin Efficiency Efficiency Std. (V) (mA/cm{circumflex over ( )}2) FF (mW/cm{circumflex over ( )}2) (%) (%) Dev. Dye/Light 0.615 4.272 0.647 72.9138 2.331315 1.660343 0.77311 L1/High 0.582 3.5024 0.622 72.9138 1.738879 0.525 1.4344 0.453 72.9138 0.467862 0.602 4.66 0.674 72.9138 2.59318 0.546 2.9492 0.53 72.9138 1.170477 0.448 0.2546 0.422 4.7431 1.014814 0.767369 0.41654 L1/Low 0.389 0.1618 0.444 4.7431 0.589035 0.351 0.042 0.874 4.7431 0.271647 0.454 0.4192 0.361 4.7431 1.448511 0.365 0.1579 0.422 4.7431 0.512838 0.576 1.856 0.368 72.9138 0.539559 1.694332 0.83466 4a + DCA/High 0.633 4.128 0.693 72.9138 2.483516 0.592 3.5484 0.715 72.9138 2.059921 0.628 3.0648 0.483 72.9138 1.274968 1.333435 4a/High 0.617 3.0688 0.536 72.9138 1.391903 0.517 0.42 0.717 4.7431 3.282437 4.366019 0.88331 4a + DCA/Low 0.562 0.6492 0.708 4.7431 5.446098 0.533 0.5312 0.732 4.7431 4.36952 0.578 0.7336 0.744 4.7431 6.651162 5.686032 4a/Low 0.561 0.5372 0.743 4.7431 4.720903 0.529 4.596 0.599 72.9138 1.997344 1.796431 9a + DCA/High 0.525 3.1476 0.704 72.9138 1.595518 0.584 2.2828 0.701 72.9138 1.281708 1.70936 0.27617 9a/High 0.643 3.2776 0.697 72.9138 2.014605 0.632 2.942 0.735 72.9138 1.874293 0.619 2.5532 0.769 72.9138 1.666833 0.471 0.42 0.812 4.7431 3.386598 4.313371 9a + DCA/Low 0.468 0.71 0.748 4.7431 5.240144 0.523 0.42 0.594 4.7431 2.7509 3.66525 0.64797 9a/Low 0.588 0.42 0.844 4.7431 4.39447 0.576 0.42 0.812 4.7431 4.141572 0.562 0.42 0.678 4.7431 3.374059 0.493 2.6276 0.699 72.9138 1.241863 1.956097 0.56854 13a + DCA/High 0.53 4.36 0.629 72.9138 1.993441 0.639 4.144 0.725 72.9138 2.632988 0.544 4.528 0.681 72.9138 2.300609 2.077432 0.17596 13a/High 0.578 3.5644 0.662 72.9138 1.870521 0.543 3.9996 0.692 72.9138 2.061165 0.422 0.3222 0.459 4.7431 1.315958 2.334279 0.74598 13a + DCA/Low 0.455 0.42 0.765 4.7431 3.082191 0.555 0.42 0.53 4.7431 2.604687 0.479 0.42 0.732 4.7431 3.104798 3.030841 0.40724 13a/Low 0.504 0.42 0.56 4.7431 2.499224 0.49 0.42 0.804 4.7431 3.488501 0.558 1.0588 0.607 68.3966 0.524327 0.345444 0.21025 5 + DCA/High 0.555 0.942 0.604 68.3966 0.461686 0.137 0.8972 0.28 68.3966 0.050319 0.184 0.6468 0.268 68.3966 0.046632 0.305319 0.19918 5/High 0.563 1.0276 0.628 68.3966 0.5312 0.509 0.778 0.584 68.3966 0.338124

    (48) Based on the table above, it is observed that the present dyes in the DSSC have 1) increased panchromatic absorption leading to improved performance at lower light levels; 2) Added redox stability and optimal electron injection kinetics owing to the incorporation of two redox robust triphenylamine donor units; and 3) improved electronic communication between interfaces as a result of the bipodal structure of the dye.

    (49) Note that all DSSCs described in the table above were made with the Z1137 electrolyte.

    (50) As many changes can be made to the alternatives without departing from the scope thereof; it is intended that all matter contained herein be considered illustrative and not in a limiting sense.