title: Copper(i) 5-phenylpyrimidine-2-thiolate complexes showing unique optical properties and high visible light-directed catalytic performance.
abstract: Solvothermal reactions of 5-phenylpyrimidine-2-thiol (5-phpymtH) with equimolar CuBr afforded one hexanuclear cluster [Cu6(μ3-5-phpymt)6] (1) along with a tetranuclear by-product [{(Cu2Br)(μ-5-phpymtH)}(μ3-5-phpymt)]2(2). A two dimensional (2D) polymer [Cu4(μ5-5-phpymt)2(μ-Br)2]n(3) was isolated from the reaction of 5-phpymtH with two equiv. of CuBr. Analogous reactions of 5-phpymtH with one or four equiv. of CuI produced one tetranuclear cluster [{Cu2(μ-5-phpymtH)(μ-5-phpymt)}(μ3-I)]2(4) and one 2D polymer [Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(5). Compound 1 possesses a water-wheel-shaped hexameric structure. Compound 2 has an H-shaped tetrameric structure. Compound 3 possesses a 2D network in which unique 1D [Cu8(μ-Br)2(μ5-5-phpymt)4]nchains are connected by μ-Br-ions. Compound 4 has another tetrameric structure in which two {Cu2(μ-5-phpymtH)2(μ-5-phpymt)} fragments are linked by a pair of μ3-I-ions. Compound 5 contains another 2D network in which hexanuclear {Cu6I2(μ4-I)2} units are linked by μ4-5-phpymt bridges. The 5-phpymt ligand shows four coordination modes: μ-κ1(S)-κ1(N) (4), μ3-κ2(S)-κ1(N) (1 and 2), μ4-κ1(N)-κ2(S)-κ1(N') (5) and μ5-κ1(N)-κ3(S)-κ1(N') (3). Complex 1 shows strong solvatochromic behaviour and displays reversible luminescence switching upon alternate addition of CF3COOH and Et3N into its CHCl3solution. Complexes 1-5 exhibit a high photocatalytic activity towards the aerobic oxidative hydroxylation of arylboronic acids to phenols under visible light irradiation. Catalyst 5 can be reused in several cycles without any obvious decay of the catalytic efficiency. These results offer an interesting insight into how the CuX/5-phpymtH molar ratios and X-ions exert great impacts on the coordination modes of the 5-phpymt-ligand, the structures of the final complexes, and the luminescence and catalytic properties.
authors.affiliation: State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu, People's Republic of China. lihx@suda.edu.cn jplang@suda.edu.cn.
authors.forename: Meng-Juan
authors.initials: MJ
authors.lastname: Zhang
authors.forename: Hong-Xi
authors.initials: HX
authors.lastname: Li
authors.forename: Hai-Yan
authors.initials: HY
authors.lastname: Li
authors.forename: Jian-Ping
authors.initials: JP
authors.lastname: Lang