2026-02-06 バッファロー大学（UB）
＜関連情報＞
- https://www.buffalo.edu/news/releases/2026/02/crystals-in-a-new-light.html
- https://pubs.acs.org/doi/full/10.1021/acs.cgd.4c00556
- https://journals.iucr.org/m/issues/2023/06/00/yc5044/index.html
ジアリールエテン系結晶固体の結晶構造ランドスケープ：包括的なCSD解析 Crystal Structure Landscape of Diarylethene-Based Crystalline Solids: A Comprehensive CSD Analysis
Xiaotong Zhang,Travis B. Mitchell,Jason B. Benedict
Crystal Growth & Design Published:Published: July 23, 2024
DOI:https://doi.org/10.1021/acs.cgd.4c00556
Abstract
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 D–D 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.
ジチエニルエテン系結晶固体の結晶構造ランドスケープに対するスカラーベースの幾何学的パラメータ化アプローチの開発 Development of a scalar-based geometric parameterization approach for the crystal structure landscape of dithienylethene-based crystalline solids
Travis B. Mitchell,Xiaotong Zhang,Ronald T. Jerozal,Yu-Sheng Chen,SuYin Wang and Jason B. Benedict
IUCrj Published:September 2023
DOI:https://doi.org/10.1107/S2052252523008060
Dithienylethenes (DTEs) are a promising class of organic photoswitches that can be used to create crystalline solids with properties controlled by light. However, the ability of DTEs to adopt multiple conformations, only one of which is photoactive, complicates the rational design of these materials. Herein, the synthesis and structural characterization of 19 crystalline solids containing a single DTE molecule are described. A novel D–D analysis of the molecular geometries obtained from rotational potential energy surface calculations and the ensemble of experimental structures were used to construct a crystal landscape for DTE. Of the 19 crystal structures, 17 contained photoinactive DTE rotamers and only 2 were photoactive. These results highlight the challenges associated with the design of these materials. Overall, the D–D analysis described herein provides rapid, effective and intuitive means of linking the molecular structure to photoactivity that could be applied more broadly to afford a general strategy for producing photoactive diarylethene-based crystalline solids.
