蒽诱导的高度扭曲金属环的形成及其晶体结构和可调组装行为。
Anthracene-induced formation of highly twisted metallacycle and its crystal structure and tunable assembly behaviors.
机构信息
State Key Laboratory Base of Novel Functional Materials and Preparation Science, School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China.
Department of Chemistry, University of Utah, Salt Lake City, UT 84112;
出版信息
Proc Natl Acad Sci U S A. 2021 Jul 6;118(27). doi: 10.1073/pnas.2102602118.
Polycyclic aromatic hydrocarbons (PAHs) continue to attract increasing interest with respect to their applications as luminescent materials. The ordered structure of the metal-organic complex facilitates the selective integration of PAHs that can be tuned to function cooperatively. Here, a unique highly twisted anthracene-based organoplatinum metallacycle was prepared via coordination-driven self-assembly. Single-crystal X-ray diffraction analysis revealed that the metallacycle was twisted through the cooperation of strong π···π stacking interactions and steric hindrance between two anthracene-based ligands. Notably, the intramolecular twist and aggregation behavior introduced restrictions to the conformational change of anthracenes, which resulted in increased emission intensity of the metallacycle in solution. The emission behaviors and suprastructures based on the highly twisted metallacycle can be modulated by the introduction of different solvents. This study demonstrates that this metallacycle with highly twisted structure is a promising candidate for sensing and bioimaging applications.
多环芳烃（PAHs）作为发光材料，其应用继续引起人们越来越多的关注。金属-有机配合物的有序结构有利于对 PAHs 的选择性整合，从而可以协同作用进行调谐。在这里，通过配位驱动的自组装制备了一种独特的高度扭曲的基于蒽的有机铂金属环。单晶 X 射线衍射分析表明，金属环通过强 π···π 堆积相互作用和两个基于蒽的配体之间的空间位阻的协同作用而扭曲。值得注意的是，分子内扭曲和聚集行为限制了蒽的构象变化，这导致金属环在溶液中的发射强度增加。通过引入不同的溶剂，可以调节基于高度扭曲金属环的发光行为和超结构。这项研究表明，这种具有高度扭曲结构的金属环是传感和生物成像应用的有前途的候选者。
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