Boosting FRET Efficiency of Chromophores with Aggregation‐Caused Quenching by a Crystallization‐Induced Precise Co‐assembly Strategy

Abstract Förster resonance energy transfer (FRET) plays a critical role in organic optoelectronic materials. However, developing facile and effective strategies to achieve high‐efficiency energy harvesting of chromophores with aggregation‐caused quenching (ACQ) remains an appealing yet challenging task, that has not yet been explored. Herein, a subtly strategy, crystallization‐induced precise co‐assembly (CIPCA) involving a molecular “lightening agent,” to effectively improve FRET efficiency of ACQ chromophores is developed. Bis(phenylethynyl)anthracene (BPA) and bis(phenylethynyl)naphthacene (BPN) with significant ACQ effect are chosen as representative FRET donor and acceptor, respectively, and weakly‐fluorescent octafluoronaphthalene (OFN) acted as the “lightening agent.” Thanks to precise co‐assembly with OFN, the PLQY of solid BPA is enhanced by 107%, and the BPN powder can be unprecedentedly lighted. More importantly, through such powerful CIPCA, the monotonous and weak emission for BPA@BPN can be remarkably regulated to colorful and much brighter ones with FRET efficiency improvement of as high as 180–270%. An in‐depth understanding of FRET regulation is elucidated through a precise correlation of the supramolecular structures and properties. Such achievements allow to successfully fabricate distinct multi‐stimuli‐responsive fluorescent patterns and highly‐emissive colorful flowers with high flexibility. This research provides an efficient strategy to improve the FRET efficiency of ACQ pairs.