State Key Laboratory of Synthetic Chemistry, Institute of Molecular Functional Materials, HKU-CAS Joint Laboratory on New Materials, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China.
HKU Shenzhen Institute of Research and Innovation, Shenzhen, 518053, China.
Angew Chem Int Ed Engl. 2016 Aug 22;55(35):10312-6. doi: 10.1002/anie.201604762. Epub 2016 Jul 28.
Copper(I) alkynyl complexes have attracted tremendous attention in structural studies, as luminescent materials, and in catalysis, and homoleptic complexes have been reported to form polymers or large clusters. Herein, six unprecedented structures of Cu(I) alkynyl complexes and a procedure to measure the cone angles of alkynyl ligands based on the crystal structures of these complexes are reported. An increase of the alkynyl cone angle in the complexes leads to a modulation of the structures from polymeric [((PhC≡CC≡C)Cu)2 (NH3 )]∞ , to a large cluster [(TripC≡CC≡C)Cu]20 (MeCN)4 , to a relatively small cluster [(TripC≡C)Cu]8 (Trip=2,4,6-iPr3 -C6 H2 ). The complexes exhibit yellow-to-red phosphorescence at ambient temperature in the solid state and the luminescence behavior of the Cu20 cluster is sensitive to acetonitrile.
铜（I）炔基配合物在结构研究、发光材料和催化领域引起了极大的关注，并且已经报道了同核配合物形成聚合物或大簇。本文报道了六个前所未有的铜（I）炔基配合物的结构，以及一种基于这些配合物晶体结构测量炔基配体锥角的方法。炔基配体的锥角增加会导致配合物结构从聚合物[((PhC≡CC≡C)Cu)2(NH3)]∞，到大型簇[(TripC≡CC≡C)Cu]20(MeCN)4，再到相对较小的簇[(TripC≡C)Cu]8(Trip=2,4,6-iPr3-C6H2)。这些配合物在固态下于室温下表现出黄色到红色磷光，并且 Cu20 簇的发光行为对乙腈敏感。
