Peters Garvin M, Tovar John D
J Am Chem Soc. 2019 Feb 20;141(7):3146-3152. doi: 10.1021/jacs.8b12617. Epub 2019 Feb 6.
The ability to externally modulate conjugated polymer optoelectronic properties is an important challenge for modern organic electronics. One attractive approach entails the incorporation of stimuli-responsive molecular systems, such as diarylethenes, into polymeric materials. Our approach involves the design of polymers possessing photochromic moieties pendant to the main conjugated chain to allow for electronic influence along the polymer backbone while avoiding substantial conformational demands that may affect solid-state performance. Herein, we report the synthesis of a series of thieno[3,4- b]thiophene (TT)-based photochromes that demonstrate drastically different optoelectronic properties upon cyclization. Experimental and computational investigations of aryl-extended model compounds provided crucial insight on the interplay between electronic structure and photochromic activity, thus allowing for the realization of pendant photoswitchable conjugated copolymers that reflect the activity found in the related model systems.
从外部调节共轭聚合物的光电特性的能力是现代有机电子学面临的一项重大挑战。一种引人注目的方法是将刺激响应分子体系，如二芳基乙烯，引入聚合材料中。我们的方法涉及设计聚合物，使其主共轭链上带有光致变色部分，以便在聚合物主链上产生电子影响，同时避免可能影响固态性能的大量构象要求。在此，我们报道了一系列基于噻吩并[3,4-b]噻吩（TT）的光致变色化合物的合成，这些化合物在环化后表现出截然不同的光电特性。对芳基扩展模型化合物的实验和计算研究为电子结构与光致变色活性之间的相互作用提供了关键见解，从而实现了能反映相关模型体系中活性的侧链光开关共轭共聚物。
