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.

中文翻译：

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利用分子识别操纵对称性破坏电荷分离


在设计功能性光捕获材料时，对对称性破坏电荷分离 （SB-CS） 的探索势在必行。然而，过去的探索仅限于共价系统，通常需要复杂/苛刻的合成，并且面临电荷转移过程的不便调节。在这里，我们提出了一个概念，该概念通过使用基于吡啶的环烷作为宿主的分子识别来调节 SB-CS 的效率。该主机经历光驱动激发态 SB-CS。通过采用具有不同前沿分子轨道能级的不同客体，我们实现了对环烷中电子转移途径的全面控制，在涉及超交换的加速 （>10 倍） 分子内 SB-CS 和主客体之间的直接分子间电子转移之间进行调节。SB-CS 效率的提高导致硫芥子气模拟物的光氧化催化活性。这项研究为利用分子识别来调整 SB-CS 提供了机会，这有可能在没有复杂的有机合成的情况下实现精确调节。