Sulfur-Bridged Terthiophene Dimers: How Sulfur Oxidation State Controls Interchromophore Electronic Coupling

Journal of the American Chemical Society
Chad D CruzChristopher J Bardeen

Abstract

Symmetric dimers have the potential to optimize energy transfer and charge separation in optoelectronic devices. In this paper, a combination of optical spectroscopy (steady-state and time-resolved) and electronic structure theory is used to analyze the photophysics of sulfur-bridged terthiophene dimers. This class of dimers has the unique feature that the interchromophore (intradimer) electronic coupling can be modified by varying the oxidation state of the bridging sulfur from sulfide (S), to sulfoxide (SO), to sulfone (SO2). Photoexcitation leads to the formation of a delocalized charge resonance state (S1) that relaxes quickly (<10 ps) to a charge-transfer state (S1*). The amount of charge-transfer character in S1* can be enhanced by increasing the oxidation state of the bridging sulfur group as well as the solvent polarity. The S1* state has a decreased intersystem crossing rate when compared to monomeric terthiophene, leading to an enhanced photoluminescence quantum yield. Computational results indicate that electrostatic screening by the bridging sulfur electrons is the key parameter that controls the amount of charge-transfer character. Control of the sulfur bridge oxidation state provides the ability to tune interchrom...Continue Reading

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Citations

Mar 2, 2016·The Journal of Physical Chemistry. a·Takao SakumaTaku Hasobe
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Oct 29, 2021·Journal of the American Chemical Society·Taylor N LewisChristopher J Bardeen

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