| Abstract |
The exploration of symmetry-breaking charge separation (SB-CS) is imperative when designing functional light-harvesting materials. Past explorations, however, have been confined to covalent systems, more often than not requiring complicated/demanding syntheses and facing inconvenient regulation of charge transfer processes. Here, we present a concept that regulates the efficiency of SB-CS through molecular recognition utilizing a pyridinium-based cyclophane as a host. This host undergoes photo-driven excited-state SB-CS. By employing different guests with distinct frontier molecular orbital energy levels, we have achieved comprehensive control of electron transfer pathways in the cyclophane, modulating between accelerated (>10-fold) intramolecular SB-CS involving superexchange and direct intermolecular electron transfer between the host and guest. The improvement in SB-CS efficiency results in catalytic activity for the photo-oxidation of a sulfur-mustard simulant. This research offers an opportunity for tuning SB-CS by utilizing molecular recognition, which holds the potential for achieving precise regulation without complicated organic syntheses. |
| Authors |
Xueze Zhao  , Ryan M. Young , Chun Tang , Guangcheng Wu , Kathryn R. Peinkofer , Yaoyao Han , Shuliang Yang , Yikang Xing , Han Han , Huang Wu , Xuesong Li  , Yuanning Feng , Ruihua Zhang , Charlotte L. Stern , Michael R. Wasielewski , J. Fraser Stoddart
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