Zhu Xiao-Zhao, Jia Tao, Guan Zong-Jie, Zhang Qian, Yang Yang
School of Chemistry and Materials Science, Jiangsu Normal University, Jiangsu 221008, China.
College of Chemistry and Chemical Engineering, Hunan University, Hunan 410012, China.
Inorg Chem. 2022 Sep 26;61(38):15144-15151. doi: 10.1021/acs.inorgchem.2c02306. Epub 2022 Sep 13.
A pair of alkynyl-diphosphine-coprotected copper(I) clusters, namely, Cu(4-MeO-PhC≡C)(dppe) [; dppe = 1,2-bis(diphenylphosphino)ethane] and Cu(H)(4-MeO-PhC≡C)(dpppe) [; dpppe = 1,5-bis(diphenylphosphino)pentane], featuring trigonal-prismatic frameworks have been synthesized by a reduction method. Their molecular structures are determined by X-ray crystallography and characterized by multiple techniques. The length of the spacer of the diphosphine ligand can directly affect the aspect ratio of the clusters. with dppe as ligands has a trigonal-prismatic core. The longer alkyl spacer of dpppe helps to elongate the trigonal-prismatic framework to form , with its trigonal-prismatic framework encapsulating a CuH unit. Electrospray ionization mass spectrometry, H NMR, and liberations of hydrogen further verify the presence of a hydride in the cluster. Density functional theory calculations help to locate the position of the hydride and understand the electronic structures of the clusters. is the first alkynyl-phosphine-coprotected copper hydride cluster. These two clusters show distinct luminescence properties. The compact is phosphorescent upon radiation, while the longer with more flexibility is nonluminous. This work enriches the family of copper hydrides and demonstrates the ligand effects in the extension of the length and structural complexity of clusters.
通过还原法合成了一对炔基二膦共保护的铜（I）簇合物，即Cu(4-MeO-PhC≡C)(dppe) [；dppe = 1,2-双（二苯基膦基）乙烷]和Cu(H)(4-MeO-PhC≡C)(dpppe) [；dpppe = 1,5-双（二苯基膦基）戊烷]，其具有三角棱柱框架。通过X射线晶体学确定了它们的分子结构，并通过多种技术进行了表征。二膦配体间隔基的长度可直接影响簇合物的长宽比。以dppe作为配体的簇合物具有三角棱柱形核心。dpppe较长的烷基间隔基有助于拉长三角棱柱框架以形成，其三角棱柱框架包裹着一个CuH单元。电喷雾电离质谱、1H NMR和氢气释放进一步证实了簇合物中存在氢化物。密度泛函理论计算有助于确定氢化物的位置并理解簇合物的电子结构。是首个炔基膦共保护的氢化铜簇合物。这两个簇合物表现出不同的发光性质。结构紧凑的在辐射时发出磷光，而具有更大灵活性的较长簇合物则不发光。这项工作丰富了氢化铜家族，并展示了配体在簇合物长度延伸和结构复杂性方面的作用。
