Zhang Xiaotong, Mitchell Travis B, Benedict Jason B
Department of Chemistry, University at Buffalo, Natural Sciences Complex, Buffalo, New York 14260-3000, United States.
Cryst Growth Des. 2024 Jul 23;24(15):6284-6291. doi: 10.1021/acs.cgd.4c00556. eCollection 2024 Aug 7.
Diarylethenes (DAEs) are an exciting class of stimulus-responsive organic molecules that exhibit electrocyclization reactions upon exposure to light, heat, or other stimuli. The rational design of DAE-based crystalline materials is, however, complicated by the presence of DAE atropisomers, only one of which is photoactive. Data mining of the CSD produced 1349 unique molecular DAE structures that were subsequently analyzed according to selected chemical and geometric attributes. Additional analyses were performed on 1078 dithienylethene (DTE) structures-the largest subgroup within the ensemble. The crystal structure landscape, based upon - parameterization and analysis, revealed a vast array of molecular geometries, many of which may not correspond to energetic minima. The analyses link various chemical and geometric parameters to isomers observed in the lattice and their reactivity; however, potential biases intrinsic to this ensemble of structures complicate the determination of causal relationships. We believe that this retrospective comprehensive analysis of DAE structures represents an important step for understanding more broadly the crystal landscape of this class of materials.
二芳基乙烯（DAEs）是一类令人兴奋的刺激响应性有机分子，在受到光、热或其他刺激时会发生电环化反应。然而，基于DAE的晶体材料的合理设计因DAE阻转异构体的存在而变得复杂，其中只有一种具有光活性。对剑桥晶体结构数据库（CSD）的数据挖掘产生了1349个独特的分子DAE结构，随后根据选定的化学和几何属性对其进行了分析。对1078个二噻吩乙烯（DTE）结构进行了额外分析，DTE是该集合中最大的子群。基于参数化和分析的晶体结构格局揭示了大量的分子几何结构，其中许多可能并不对应于能量最小值。这些分析将各种化学和几何参数与晶格中观察到的异构体及其反应性联系起来；然而，这一结构集合固有的潜在偏差使因果关系的确定变得复杂。我们认为，对DAE结构的这种回顾性综合分析是更广泛地理解这类材料晶体格局的重要一步。
