Vanga Mukundam, Diroll Benjamin T, Muñoz-Castro Álvaro R, Dias H V Rasika
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019, USA.
Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Dalton Trans. 2023 Nov 14;52(44):16356-16363. doi: 10.1039/d3dt03167e.
Successful synthesis has been reported of 4-MesB-3,5-(CF)PzH and 4-MesB-3,5-(CF)PzH bearing sterically demanding diarylboron moieties at the pyrazole ring 4-position, and their corresponding copper(I) pyrazolate complexes. They show visible blue photoluminescence in solution. The X-ray crystal structures revealed that the fluorinated {[4-BMes-3,5-(CF)Pz]Cu} crystallizes as discrete trinuclear molecules whereas as the non-fluorinated {[4-BMes-3,5-(CH)Pz]Cu} forms dimers of trimers with two close inter-trimer Cu⋯Cu separations. The solid {[4-BMes-3,5-(CF)Pz]Cu} featuring a sterically confined CuN core displays bright blue phosphorescence while {[4-BMes-3,5-(CH)Pz]Cu}, which is a dimer of a trimer, is a red phosphor at room temperature. This work illustrates the modulation of photo-physical properties of metal pyrazolates by adjusting the supporting ligand steric features and introducing secondary diarylboron luminophores. Computational analysis of the structures and photophysical properties of copper complexes are also presented.
据报道，已成功合成了4-MesB-3,5-(CF)PzH和在吡唑环4位带有空间位阻较大的二芳基硼部分的4-MesB-3,5-(CF)PzH及其相应的铜(I)吡唑酸盐配合物。它们在溶液中呈现出可见的蓝色光致发光。X射线晶体结构表明，氟化的{[4-BMes-3,5-(CF)Pz]Cu}以离散的三核分子形式结晶，而非氟化的{[4-BMes-3,5-(CH)Pz]Cu}形成三聚体的二聚体，三聚体之间有两个紧密的Cu⋯Cu间距。具有空间受限的CuN核心的固体{[4-BMes-3,5-(CF)Pz]Cu}显示出亮蓝色磷光，而作为三聚体二聚体的{[4-BMes-3,5-(CH)Pz]Cu}在室温下是红色磷光体。这项工作说明了通过调节配体的空间特征和引入二级二芳基硼发光体来调节金属吡唑酸盐的光物理性质。还介绍了铜配合物结构和光物理性质的计算分析。
