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

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···TiO 2 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···TiO 2 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···TiO 2 adsorption energy calculations corroborate their applicability, demonstrating themore » potential of cyanine dyes in DSC research.« less
Authors:
 [1] ;  [2] ;  [3] ;  [1]
  1. Univ. of Cambridge (United Kingdom). Cavendish Lab.
  2. Univ. of Cambridge (United Kingdom). Cavendish Lab.; Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of Cambridge (United Kingdom). Cavendish Lab.; Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW (Australia)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Molecular Systems Design & Engineering
Additional Journal Information:
Journal Volume: 1; Journal Issue: 1; Journal ID: ISSN 2058-9689
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
Engineering and Physical Sciences Research Council (EPSRC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 14 SOLAR ENERGY
OSTI Identifier:
1352871

Pepe, Giulio, Cole, Jacqueline M., Waddell, Paul G., and McKechnie, Scott. Molecular engineering of cyanine dyes to design a panchromatic response in Co-sensitized dye-sensitized solar cells. United States: N. p., Web. doi:10.1039/C6ME00014B.
Pepe, Giulio, Cole, Jacqueline M., Waddell, Paul G., & McKechnie, Scott. Molecular engineering of cyanine dyes to design a panchromatic response in Co-sensitized dye-sensitized solar cells. United States. doi:10.1039/C6ME00014B.
Pepe, Giulio, Cole, Jacqueline M., Waddell, Paul G., and McKechnie, Scott. 2016. "Molecular engineering of cyanine dyes to design a panchromatic response in Co-sensitized dye-sensitized solar cells". United States. doi:10.1039/C6ME00014B. https://www.osti.gov/servlets/purl/1352871.
@article{osti_1352871,
title = {Molecular engineering of cyanine dyes to design a panchromatic response in Co-sensitized dye-sensitized solar cells},
author = {Pepe, Giulio and Cole, Jacqueline M. and Waddell, Paul G. and McKechnie, Scott},
abstractNote = {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.},
doi = {10.1039/C6ME00014B},
journal = {Molecular Systems Design & Engineering},
number = 1,
volume = 1,
place = {United States},
year = {2016},
month = {4}
}

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