Yao Liao-Yuan, Yam Vivian Wing-Wah
Institute of Molecular Functional Materials, State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P.R. China.
J Am Chem Soc. 2021 Feb 17;143(6):2558-2566. doi: 10.1021/jacs.0c11891. Epub 2021 Feb 3.
A decanuclear gold(I)-sulfido complex, [(L)AuS]Cl (, where L = 4,5-bis(diphenylphosphanyl)-2-1,2,3-triazole), assembled from the reaction of HS with the chlorogold(I) precursor obtained from the click reaction of [dppa(AuCl)] (where dppa = 1,2-bis(diphenylphosphino)acetylene) with NaN, is shown to display a bright dual green and red emission in the solid state. Single crystal X-ray diffraction (SCXRD) studies indicate a gold(I) cluster-based framework assembled through intermolecular halogen···hydrogen bonds as well as other weak interactions. The framework of is found to display high stability toward solvent molecules, with capability to encapsulate solvent molecules, such as benzene and cyclohexane, inside the crystal lattice voids via a single-crystal-to-single-crystal (SCSC) transformation. With different degrees of influence on the dual green and red emission, crystalline solids of exhibit remarkable solvatochromic luminescence in the presence of benzene and cyclohexane. Notably, due to the size confinement of the lattice cavities, the solids exhibit a high selectivity (>95%) toward benzene in a mixture of equimolar concentration of benzene and cyclohexane. This work has demonstrated the promising capability of gold(I)-sulfido cluster frameworks to serve as luminescent functional materials for the separation of benzene and cyclohexane.
一种十核金(I)-硫代配合物,[(L)AuS]Cl(其中L = 4,5-双(二苯基膦基)-2-1,2,3-三唑),由HS与通过[dppa(AuCl)](其中dppa = 1,2-双(二苯基膦基)乙炔)与NaN的点击反应得到的氯金(I)前体反应组装而成,在固态下显示出明亮的绿色和红色双重发射。单晶X射线衍射(SCXRD)研究表明,通过分子间卤素···氢键以及其他弱相互作用组装形成了基于金(I)簇的框架。发现该框架对溶剂分子具有高稳定性,能够通过单晶到单晶(SCSC)转变将苯和环己烷等溶剂分子封装在晶格空隙内。在苯和环己烷存在下,配合物的晶体固体对双重绿色和红色发射有不同程度的影响,表现出显著的溶剂致变色发光。值得注意的是,由于晶格空腔的尺寸限制,配合物固体在等摩尔浓度的苯和环己烷混合物中对苯表现出高选择性(>95%)。这项工作证明了金(I)-硫代簇框架作为用于苯和环己烷分离的发光功能材料的潜力。