Molecular engineering of cyanine dyes to design a panchromatic response in Co-sensitized dye-sensitized solar cells

Pepe, Giulio; Cole, Jacqueline M.; Waddell, Paul G.; McKechnie, Scott

doi:10.1039/C6ME00014B

Molecular engineering of cyanine dyes to design a panchromatic response in Co-sensitized dye-sensitized solar cells

Journal Article · Tue Apr 05 00:00:00 EDT 2016 · Molecular Systems Design & Engineering

DOI:https://doi.org/10.1039/C6ME00014B· OSTI ID:1352871

Pepe, Giulio ^[1]; Cole, Jacqueline M. ^[2]; Waddell, Paul G. ^[3]; McKechnie, Scott ^[1]

Univ. of Cambridge (United Kingdom). Cavendish Lab.
Univ. of Cambridge (United Kingdom). Cavendish Lab.; Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Cambridge (United Kingdom). Cavendish Lab.; Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW (Australia)

Cyanines are optically tunable dyes with high molar extinction coefficients, suitable for applications in co-sensitized dye-sensitized solar cells (DSCs); yet, barely thus applied. This might be due to the lack of a rational molecular design strategy that efficiently exploits cyanine properties. This study computationally re-designs these dyes, to broaden their optical absorption spectrum and create dye···TiO₂ binding and co-sensitization functionality. This is achieved via a stepwise molecular engineering approach. Firstly, the structural and optical properties of four parent dyes are experimentally and computationally investigated: 3,3’-diethyloxacarbocyanine iodide, 3,3’-diethylthiacarbocyanine iodide, 3,3’-diethylthiadicarbocyanine iodide and 3,3’-diethylthiatricarbocyanine iodide. Secondly, the molecules are theoretically modified and their energetics are analyzed and compared to the parent dyes. A dye···TiO₂ anchoring group (carboxylic or cyanoacrylic acid), absent from the parent dyes, is chemically substituted at different molecular positions to investigate changes in optical absorption. We find that cyanoacrylic acid substitution at the para-quinoidal position affects the absorption wavelength of all parent dyes, with an optimal bathochromic shift of ca. 40 nm. The theoretical lengthening of the polymethine chain is also shown to effect dye absorption. Two molecularly engineered dyes are proposed as promising co-sensitizers. Finally, corresponding dye···TiO₂ adsorption energy calculations corroborate their applicability, demonstrating the potential of cyanine dyes in DSC research.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: Engineering and Physical Sciences Research Council (EPSRC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1352871

Journal Information:: Molecular Systems Design & Engineering, Journal Name: Molecular Systems Design & Engineering Journal Issue: 1 Vol. 1; ISSN 2058-9689

Country of Publication:: United States

Language:: English

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