β-Functionalized Push-Pull Porphyrin Sensitizers in Dye-Sensitized Solar Cells: Effect of π-Conjugated Spacers

Masatoshi Ishida, Daesub Hwang, Zhan Zhang, Yung Ji Choi, Juwon Oh, Vincent M. Lynch, Dong Young Kim, Jonanthan L. Sessler, Dongho Kim

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Abstract

A series of new β-functionalized push-pull-structured porphyrin dyes were synthesized so as to investigate the effect of the π-conjugated spacer on the performance of dye-sensitized solar cells (DSSCs). Suzuki- and Heck-type palladium-catalyzed coupling methodologies were used to obtain various β-functionalized porphyrins and β-benzoic acid (ZnPHn) and β-vinylbenzoic acid (ZnPVn) derivatives from β-borylated porphyrin precursors. Photophysical studies of the resulting porphyrins revealed a clear dependence on the nature of the β linker. In particular, it was found that a β-vinylene linkage perturbs the electronic structure of the porphyrin core; this is less true for a β-phenyl linkage. Theoretical analyses provided support for the intrinsic intramolecular charge-transfer character of the β-functionalized, push-pull porphyrins of this study. The extent of charge transfer depends on the nature of the β-conjugated linkage. The photovoltaic performances of the cells sensitized with β-phenylenevinylene ZnPVn exhibited higher power conversion efficiency values than those bearing β-phenyl linkages (ZnPHn). This was ascribed to differences in light-harvesting efficiency. Furthermore, compared to the use of a standard iodine-based electrolyte, the DSSC performance of cells made from the present porphyrins was improved by more than 1% upon using a cobalt(II/III)-based electrolyte. Under standard AM 1.5 illumination, the highest efficiency, 8.2%, was obtained by using cells made from the doubly β-butadiene-linked porphyrin.

Original languageEnglish
Pages (from-to)2967-2977
Number of pages11
JournalChemSusChem
Volume8
Issue number17
DOIs
Publication statusPublished - 2015 Sep 1

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All Science Journal Classification (ASJC) codes

  • Environmental Chemistry
  • Chemical Engineering(all)
  • Materials Science(all)
  • Energy(all)

Cite this

Ishida, M., Hwang, D., Zhang, Z., Choi, Y. J., Oh, J., Lynch, V. M., Kim, D. Y., Sessler, J. L., & Kim, D. (2015). β-Functionalized Push-Pull Porphyrin Sensitizers in Dye-Sensitized Solar Cells: Effect of π-Conjugated Spacers. ChemSusChem, 8(17), 2967-2977. https://doi.org/10.1002/cssc.201500085