journal article·2020-08-06

Molecular Origins of Photoinduced Backward Intramolecular Charge Transfer

Mengyao Hao, Weijie Chi, Chao Wang, Zhaochao Xu, Zesheng Li, Xiaogang Liu

The Journal of Physical Chemistry C· Volume 124· Issue 31
Publisher page

Abstract

Intramolecular charge transfer (ICT) is a fundamental process in photochemistry, during which charge flows from a donor (D) to an acceptor (A). In (probably) most dyes, ICT is enhanced upon photoexcitation (namely, forward ICT or FICT), endowing these compounds with positive solvatochromism. Yet, many dyes display negative solvatochromism, suggesting backward ICT (BICT). That is, a significant charge separation from D to A is achieved in the ground state, but charge transports back from A to D upon photoexcitation, leading to a reduced dipole moment in the excited state. In contrast to the well-studied FICT systems, molecular design guidelines to realize BICT remain elusive, precluding potential applications. In this paper, we showed that BICT could be achieved by incorporating double donors and double acceptors with a quinoid π-bridge. The establishment of the BICT design rules not only deepens our understanding of charge transfer but also inspires future applications (i.e., nonlinear optics).
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Research context

OpenAlex topics: Photochemistry and Electron Transfer Studies · Photochromic and Fluorescence Chemistry · Radical Photochemical Reactions

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China

Fluorescence Research Group, Singapore University of Technology and Design, Singapore 487372, Singapore

CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China

Funding

Beijing Institute of Technology · National Natural Science Foundation of China · SUTD-MIT International Design Centre, Singapore University of Technology and Design · Beijing Key Laboratory for Chemical Power Source and Green Catalysis, Beijing Institute of Technology

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