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Title: Photoexcited Phenyl Ring Twisting in Quinodimethane Dyes Enhances Photovoltaic Performance in Dye-Sensitized Solar Cells

Abstract

Four metal-free organic quinodimethane-based dyes, which represent molecular building blocks for a new class of DSSC dyes, were studied here with the objective to improve their photovoltaic performance via molecular engineering strategies. Such strategies can only be systematic and successful if they are derived from knowledge-based paradigms that relate individual aspects of the molecular structure for a given class of dyes to their photovoltaic properties. The optical and electrochemical properties of these dyes were investigated experimentally by UV–vis absorption and emission spectroscopy, as well as cyclic voltammetry and electrochemical impedance spectroscopy. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations on these dyes complement these experiments. Among other results, this concerted experimental and computational study revealed that the dialkylaminophenyl moiety in these dyes exhibits a large twist as a result of its ground-to-excited-state optical transition. In particular, a near-perpendicular (88.98°) twist of the dimethylaminophenyl moiety relative to the π-bridging unit that connects the three aryl rings in 2 was observed upon formation of its photo-excited-state structure. Moreover, it was discovered that 2 affords the highest V OC and power-conversion efficiency (PCE) values among these dyes. The particularly high PCE for 2 was found to be due to this twisting ofmore » the phenyl ring, which blocks the pathway of electrons from TiO 2 to the donor, and hence suppresses undesirable electron recombination at the dye···TiO 2 interface. This diode-like effect minimizes undesirable electron-recombination effects and represents an unprecedented structure–property relationship that should be useful for the molecular engineering of larger chromophores in this class of dyes for DSSC applications.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [3]
  1. Univ. of Cambridge (United Kingdom). Cavendish Lab.
  2. Univ. of Cambridge (United Kingdom). Dept. of Chemical Engineering and Biotechnology. Cavendish Lab.; STFC Rutherford Appleton Lab., Didcot (United Kingdom). ISIS Neutron and Muon Source; Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of Hyogo, Himeji (Japan). Graduate School of Engineering
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Cambridge (United Kingdom)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); 1851 Royal Commission (United Kingdom)
OSTI Identifier:
1493922
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Energy Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 3; Journal ID: ISSN 2574-0962
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; diode-like effect; dye-sensitized solar cell; molecular engineering; phenyl ring twist; photovoltaic performance; quinodimethane-based dyes

Citation Formats

Gong, Yun, Cole, Jacqueline M., Ozoe, Hiroaki, and Kawase, Takeshi. Photoexcited Phenyl Ring Twisting in Quinodimethane Dyes Enhances Photovoltaic Performance in Dye-Sensitized Solar Cells. United States: N. p., 2018. Web. doi:10.1021/acsaem.7b00244.
Gong, Yun, Cole, Jacqueline M., Ozoe, Hiroaki, & Kawase, Takeshi. Photoexcited Phenyl Ring Twisting in Quinodimethane Dyes Enhances Photovoltaic Performance in Dye-Sensitized Solar Cells. United States. doi:10.1021/acsaem.7b00244.
Gong, Yun, Cole, Jacqueline M., Ozoe, Hiroaki, and Kawase, Takeshi. Tue . "Photoexcited Phenyl Ring Twisting in Quinodimethane Dyes Enhances Photovoltaic Performance in Dye-Sensitized Solar Cells". United States. doi:10.1021/acsaem.7b00244. https://www.osti.gov/servlets/purl/1493922.
@article{osti_1493922,
title = {Photoexcited Phenyl Ring Twisting in Quinodimethane Dyes Enhances Photovoltaic Performance in Dye-Sensitized Solar Cells},
author = {Gong, Yun and Cole, Jacqueline M. and Ozoe, Hiroaki and Kawase, Takeshi},
abstractNote = {Four metal-free organic quinodimethane-based dyes, which represent molecular building blocks for a new class of DSSC dyes, were studied here with the objective to improve their photovoltaic performance via molecular engineering strategies. Such strategies can only be systematic and successful if they are derived from knowledge-based paradigms that relate individual aspects of the molecular structure for a given class of dyes to their photovoltaic properties. The optical and electrochemical properties of these dyes were investigated experimentally by UV–vis absorption and emission spectroscopy, as well as cyclic voltammetry and electrochemical impedance spectroscopy. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations on these dyes complement these experiments. Among other results, this concerted experimental and computational study revealed that the dialkylaminophenyl moiety in these dyes exhibits a large twist as a result of its ground-to-excited-state optical transition. In particular, a near-perpendicular (88.98°) twist of the dimethylaminophenyl moiety relative to the π-bridging unit that connects the three aryl rings in 2 was observed upon formation of its photo-excited-state structure. Moreover, it was discovered that 2 affords the highest VOC and power-conversion efficiency (PCE) values among these dyes. The particularly high PCE for 2 was found to be due to this twisting of the phenyl ring, which blocks the pathway of electrons from TiO2 to the donor, and hence suppresses undesirable electron recombination at the dye···TiO2 interface. This diode-like effect minimizes undesirable electron-recombination effects and represents an unprecedented structure–property relationship that should be useful for the molecular engineering of larger chromophores in this class of dyes for DSSC applications.},
doi = {10.1021/acsaem.7b00244},
journal = {ACS Applied Energy Materials},
number = 3,
volume = 1,
place = {United States},
year = {2018},
month = {2}
}

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