Ni(II)/Cu(I) based coordination polymers with heterofunctional ligands integrating pyridine and pyrimidinethione structural motifs

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• 作者：Hai-Bin Zhu ; ^{zhuhaibin@seu.edu.cn" class="auth_mail" title="E-mail the corresponding author} ; Yu-Zhen Wei ; Lei Liang
• 关键词：N-heterocyclic thioamide ; S&ndash ; S oxidative coupling ; Crystal structure ; Band gap ; Coordination polymers
• 刊名：Polyhedron
• 出版年：2016
• 出版时间：18 April 2016
• 年：2016
• 卷：109
• 期：Complete
• 页码：53-58
• 全文大小：1960 K

文摘

Two coordination polymers with the heterofunctional ligand 4-PPT (4-(pyridin-4-yl)pyrimidine-2-thiol), {[Ni(4-PPT)₂]·2(DMF)}_n (1) and {[Cu₂(4-PPT)₂]·2(DMF)}_n (2), have been isolated by reaction with Ni(OAc)₂ and CuBr₂, respectively. 1 shows a two-dimensional (2-D) layered structure with a 4-connected sql topology wherein the 4-PPT ligand exhibits a uniform μ₂-1, κS κN_(pyrimidine): 2, κN_(pyridine) bridging mode. 2 also features an sql net based on a unique Cu^I₄S₄ cluster in which the 4-PPT ligand adopts two kinds of coordination modes, viz. μ₃-1, κN_(pyrimidine): 2,3, κS and μ₄-1, κN_(pyrimidine): 2,3, κS: 4, κN_(pyridine). For comparison, the reaction of CuBr₂ with 3-PPT (4-(pyridin-3-yl)pyrimidine-2-thiol, an isomer of 4-PPT) under the same conditions was also examined, which yielded a 2-D Cu(I)-based coordination polymer with the 6³-hcb topology, [CuBr(3-ppds)]_n (3) (3-ppds = di(4-(pyridin-3-yl)pyrimidin-2-yl)disulfide). In 3,3-ppds was in situ generated from 3-PPTvia an S–S oxidative coupling reaction, concurrent with in situ reduction Cu^II–Cu^I. UV–Vis diffuse reflectance and luminescence spectra have been measured for 1 and 2 in order to compare their photophysical properties.