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Unique Reversible Crystal-to-Crystal Phase Transition—Structural and Functional Properties of Fused Ladder Thienoarenes
Chemistry of Materials ( IF 7.2 ) Pub Date : 2017-09-07 00:00:00 , DOI: 10.1021/acs.chemmater.7b01226
Yuichiro Abe 1, 2, 3 , Victoria Savikhin 4 , Jun Yin 5 , Andrew C. Grimsdale 1 , Cesare Soci 6 , Michael F. Toney 4 , Yeng Ming Lam 1
Affiliation  

Donor–acceptor type molecules based on fused ladder thienoarenes, indacenodithiophene (IDT), and dithienocyclopenta–thienothiophene (DTCTT), coupled with benzothiadiazole, are prepared, and their solid-state structures are investigated. They display a rich variety of solid phases ranging from amorphous glass states to crystalline states, upon changes in the central aromatic core and side group structures. Most notably, the DTCTT-based derivatives showed reversible crystal-to-crystal phase transitions in heating and cooling cycles. Unlike what has been seen in π-conjugated molecules, variable temperature XRD revealed that structural change occurs continuously during the transition. A columnar self-assembled structure with slip-stacked π–π interaction is proposed to be involved in the solid state. This research provides the evidence of unique structural behavior of the DTCTT-based molecules through the detailed structural analysis. This unique structural transition paves the way for these materials to have self-healing of crystal defects, leading to improved optoelectronic properties.

中文翻译:

独特的可逆晶体到晶体的相变—熔融梯形硫杂芳烃的结构和功能特性

制备了基于稠合梯形硫杂芳烃,茚并二噻吩(IDT)和二硫代环戊五烷-噻吩并噻吩(DTCTT)并结合苯并噻二唑的供体-受体型分子,并研究了它们的固态结构。当中心芳族核和侧基结构发生变化时,它们显示出从非晶态玻璃态到结晶态的丰富多样的固相。最值得注意的是,基于DTCTT的衍生物在加热和冷却循环中显示出可逆的晶相转变。与在π共轭分子中观察到的不同,可变温度XRD显示出结构变化在过渡过程中连续发生。提出了一种具有滑移堆积的π-π相互作用的圆柱状自组装结构,该结构涉及固态。这项研究通过详细的结构分析为基于DTCTT的分子的独特结构行为提供了证据。这种独特的结构转变为这些材料具有晶体缺陷的自我修复铺平了道路,从而改善了光电性能。
更新日期:2017-09-07
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