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Solvent dependence of the charge-transfer properties of a quaterthiophene–anthraquinone dyad
Authors:Jiandi Wan  Amy Ferreira  Wei Xia  Chak Him Chow  Kensuke Takechi  Prashant V Kamat  Guilford Jones II  Valentine I Vullev  
Institution:

aDepartment of Bioengineering, University of California, Riverside, CA 92521, United States

bDepartment of Chemistry and Photonics Center, Boston University, Boston, MA 02215, United States

cRadiation Laboratory, Departments of Chemistry and Biochemistry and Chemical and Biomolecular Engineering, University of Notre Dame, IN 46556, United States

Abstract:An electron donor–acceptor dyad (quaterthiophene–anthraquinone) mediates ultrafast intramolecular photoinduced charge separation and consequent charge recombination when in polar or moderately polar solvents. Alternatively, non-polar media completely impedes the initial photoinduced electron transfer by causing enough destabilization of the charge-transfer state and shifting its energy above the energy of the lowest locally excited singlet state. Furthermore, femtosecond transient-absorption spectroscopy reveals that for the solvents mediating the initial photoinduced electron-transfer process, the charge recombination rates were slower than the rates of charge separation. This behavior of donor–acceptor systems is essential for solar-energy-conversion applications. For the donor–acceptor dyad described in this study, the electron-transfer driving force and reorganization energy place the charge-recombination processes in the Marcus inverted region.
Keywords:Oligothiophene  Quinone  Electron transfer  Charge separation  Charge recombination  Fluorescence quenching  Laser flash photolysis  Charge-transfer rate  Rehm weller equation  Born equation
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