Halogen functionalized D–A–D-type unsymmetrical squaraine dyes for dye-sensitized solar cells

Nawghare, Indrajeet S.; Singh, Ambarish Kumar; Maibam, Ashakiran; Deshmukh, Shivdeep Suresh; Krishnamurty, Sailaja; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj

doi:10.1039/d3ma00277b

Cited by 7 publications

(7 citation statements)

References 52 publications

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“…The indoline derivatives were further alkylated with 1-iodododecane to afford the corresponding indolium salts (Fischer’s base), 4 . Furthermore, Pd-catalyzed C–N bond formation between bromo-derivative of indolium salt, 4e , and diphenylamine under Buchwald–Hartwig reaction condition afforded the diphenylamine-functionalized Fishcer’s base 4ee (Scheme a). Condensing the functionalized Fischer’s base, 4 , with carboxylic acid-containing semisquaric acid, 5 , under azeotropic removal water experimental condition provided the targeted squaraine dyes, 6a – e in moderate yields (Scheme b).…”

Section: Results and Discussionmentioning

confidence: 99%

“…Compounds 2 , 3b , 3e , 4e , and 5 are reported from our research group. Hydrazine derivatives 1a–1e and 1-iodododecane are commercially available.…”

Section: Results and Discussionmentioning

confidence: 99%

“… Started with (4-bromophenyl) hydrazine hydrochloride (0.5 g, 2.23 mmol) and 3-decylpentadecan-2-one (1.06 g, 2.90 mmol). The reaction mixture was purified by column chromatography (SiO 2 , 100–200 mesh, 1% ethyl acetate, and 99% pet.…”

Section: Results and Discussionmentioning

confidence: 99%

“…1 H NMR (CDCl 3 , 400 MHz): δ 8.07 (d, J = 8.4 Hz, 1H), 7.99 (dd, J = 8.4 Hz, 1.25 Hz, 1H), 7.81 (d, J = 1.25 Hz, 1H), 4.96 (t, J = 7.5 Hz, 2H), 3.20 (s, 3H), 2.18 (m, 2H), 1.92 (m, 2H) 1.69 (b, 2H), 1.48 (m, 2H), 1.24−1.16 (b, 46H), 0.86 (m, 11H), 0.72 (m, 2H). 13 43 Starting materials were 3e (0.56 g, 1.08 mmol) and 1-iodododecane (0.41 g, 1.40 mmol). Yield: 0.62 g, 70%.…”

Section: Synthesis Of 5-cyano-3-decyl-13-didodecyl-2methyl-3h-indol-1...mentioning

confidence: 99%

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Steric and Electronic Effect in Unsymmetrical Squaraine Dyes for Dye-Sensitized Solar Cells

Nawghare,

Singh,

Maibam

et al. 2023

J. Phys. Chem. C

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Functionalizing the light harvesting sensitizers with additional electron-donating or -withdrawing groups is a potential approach to modulate the photophysical and electrochemical properties which in-turn optimizes the driving force associated with the charge injection and dye-regeneration processes at the dye-TiO 2 / electrolyte interface and the photovoltaic device performance in dyesensitized solar cells (DSSCs). Furthermore, modulated electronic levels of the dyes provide an opportunity to reduce the overpotential associated with the dye-regeneration process and make the dye-TiO 2 interface compatible with various electrolytes. Furthermore, an in-built steric feature by means of introducing linear/branched alkyl groups in the sensitizer is important in controlling the aggregation of dyes on the TiO 2 surface. Hence, to integrate both steric and electronic properties, a series of alkyl group-wrapped unsymmetrical squaraine dyes (SQ-X) with electron-donating and -withdrawing groups have been designed, synthesized, and utilized for DSSC device fabrication. These dyes are functionalized with alkyl groups at both sp 3 -C and N-atoms of the indoline donor moiety at the nonanchoring side to have a similar steric feature. Photophysical and electrochemical studies revealed that the HOMO and LUMO energy levels of the SQ-X series of dyes have been modulated systematically with sufficient driving forces for both charge injection and dye-regeneration processes with iodolyte (I − /I 3 − ) electrolyte. In the presence of electron-donating groups in SQ-X (where X = −NPh 2 and −OMe), the HOMO energy levels are less positive than SQ-H, whereas the presence of electron-withdrawing groups such as −CO 2 Me, − CN, and −NO 2 pushed the HOMO energy levels toward more positive potentials. Enhanced photovoltaic performances have been obtained for the dyes containing electron-donating groups, where the dye with the −NPh 2 group showed a maximum of η 7.03% (V OC 708 mV, J SC 13.16 mA cm −2 , and ff 78%). The dye with the strong electron-withdrawing group −NO 2 showed an efficiency of 1.49% (V OC = 634 mV, J SC = 3.13 mA cm −2 , and ff 75%). As the dyes with the electron-withdrawing group possess deep positive HOMO energy levels, the DSSC device characterization has been investigated with the Cu +/2+ redox shuttle. The reduced device performance of electron-withdrawing-group-containing dyes is due to the unfavored charge distribution in the LUMO compared to the presence of electron-donating-group-containing dyes, and it was supported by the difference in the charge injection efficiency.

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Section: Results and Discussionmentioning

confidence: 99%

“…Compounds 2 , 3b , 3e , 4e , and 5 are reported from our research group. Hydrazine derivatives 1a–1e and 1-iodododecane are commercially available.…”

Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Section: Synthesis Of 5-cyano-3-decyl-13-didodecyl-2methyl-3h-indol-1...mentioning

confidence: 99%

See 2 more Smart Citations

Steric and Electronic Effect in Unsymmetrical Squaraine Dyes for Dye-Sensitized Solar Cells

Nawghare,

Singh,

Maibam

et al. 2023

J. Phys. Chem. C

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“…Metal‐free organic sensitizers have attracted more attention of researchers because of facile synthesis, low manufacturing cost, high molar coefficient, and ideal to harvest indoor light and for building integrated photovoltaic device, and self‐powered Internet of Things (IoT) 25,26 . Various architectures of metal‐free organic sensitizers D‐A, 27,28 D‐π‐A, 29–31 D‐A‐π‐A, 32–35 and D‐A‐D, 11,12,36–42 have been utilized to harvest light within the visible and NIR regions. Few of the metal free organic dyes were achieved DSSC efficiency between of 10–13.6% with cobalt based electrolyte in standard AM 1.5G sunlight 43,44 .…”

Section: Introductionmentioning

confidence: 99%

Far‐red active unsymmetrical squaraine dyes containing N‐arylated indoline donors for dye sensitized solar cells

Jadhav,

Singh,

Pandya

et al. 2024

Photochem & Photobiology

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Squaraine dyes possess sharp far‐red active transition with high extinction coefficient and form aggregates on TiO2 surface. Aggregation of dyes on TiO2 has been considered as a detrimental factor for DSSC device performance, which can be controlled by appending alkyl groups to the dye structures. Hence by integrating alkylated (alkyl groups with both in‐plane and out‐of‐plane) aryl group with indoline moiety to make it compatible with other electrolytes and for controlling the dye‐aggregation, a series of squaraine acceptor‐based dyes SQA4‐6 have been designed and synthesized. SQA4‐6 dyes showed absorption between 642 and 653 nm (λmax), photophysical and electrochemical studies indicated that the HOMO energy levels of this sets of dyes are well aligned with the potentials of I−/ and [Co(bpy)3]2+/3+ redox shuttles for better dye regeneration process. DSSC device efficiency of 3% has been achieved for SQA5 dye with iodolyte (I−/) electrolyte in the presence of 0.3 mM of chenodeoxycholic acid (CDCA). The IPCE profile of DSSC device fabricated with SQA4‐6 dyes indicated the contribution of aggregated structures for the photocurrent generation.

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Far-red active squaraine dye-sensitized photoanode for dye-sensitized solar cells with a copper (II/I) electrolyte

Nawghare,

Deshmukh,

Joshi

et al. 2025

Journal of Photochemistry and Photobiology A: Chemistry

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Halogen functionalized D–A–D-type unsymmetrical squaraine dyes for dye-sensitized solar cells

Abstract: Development of sensitizers with the D-A-D architecture with indoline, and squaric acid as donors and acceptor, respectively are attractive towards achieving the high dye-sensitized solar cells (DSSCs) efficiency due to...

Cited by 7 publications

References 52 publications

Steric and Electronic Effect in Unsymmetrical Squaraine Dyes for Dye-Sensitized Solar Cells

Steric and Electronic Effect in Unsymmetrical Squaraine Dyes for Dye-Sensitized Solar Cells

Far‐red active unsymmetrical squaraine dyes containing N‐arylated indoline donors for dye sensitized solar cells

Far-red active squaraine dye-sensitized photoanode for dye-sensitized solar cells with a copper (II/I) electrolyte

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