Abstract
Excited-state symmetry breaking in multipolar molecules emerged as a novel photophysical phenomenon several years ago, when it was experimentally demonstrated and tracked in real time with the help of ultrafast infrared spectroscopy. Since then, significant effort has been devoted to understanding its mechanism, universality, and the possibilities for tuning by various means. In this work we describe most up-to-date understanding of this phenomenon, diverse ways to observe and control it, and how it leads to asymmetrical excited-state reactivity in nominally symmetric molecules that can be harnessed to achieve asymmetrical photochemistry in both intra- and intermolecular reactions.
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