Zhou Rui-Sha, Zhang Xiao-Yu, Fu Jin, Xin Li-Dong, Jiao Wei-Zhou, Song Jiang-Feng
Department of Chemistry, North University of China, Taiyuan, Shanxi 030051, P. R. China.
Dalton Trans. 2021 Apr 7;50(13):4567-4576. doi: 10.1039/d1dt00322d. Epub 2021 Mar 17.
A hexagonal prismatic CuS cluster exhibits excellent near-infrared fluorescence properties due to its short Cu-Cu bonds, however, the construction of CuS cluster-based compounds with extended structures is still a challenge. Here, four new CuS cluster-based coordination compounds, formulated as Cu(pymt) (1), {(CuCN)[Cu(mpymt)]} (2), {(CuSCN)[Cu(mpymt)]} (3) and {(CuCN)[Cu(dmpymt)]·CHCN} (4) (Hpymt = pyrimidine-2-thiolate, Hmpymt = 4-methyl-pyrimidine-2-thione and Hdmpymt = 4,6-dimethylpyrimidine-2-thione), have been synthesized through the reactions of mercaptopyrimidine derivatives and CuCN or CuSCN under solvo-thermal conditions and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, elemental analysis, and thermal gravimetric analysis. Single-crystal X-ray diffraction analysis reveals that compound 1 is a zero-dimensional Cu(pymt) molecule containing a distorted pseudo-hexagonal prismatic CuS core. Compounds 2 and 4 with isomorphic frameworks but different organic linkers show a rare three-dimensional framework with nor topology constructed from Cu(mpymt) units and one-dimensional chiral [Cu(CN)] chains; compared with compound 2, a more hydrophobic one-dimensional channel in compound 4 is observed due to the increase of the methyl groups on the pyrimidine ligand, in which acetonitrile molecules are filled in the channels of compound 4. Compound 3 shows a rare two-dimensional layer constructed from Cu(mpymt) units and one-dimensional puckered (CuSCN) chains. For the first time, CuS clusters are connected to one-dimensional inorganic CuCN (or CuSCN) chains through mercaptopyrimidine derivatives to obtain extended arrays in compounds 2-4. The crystals of compounds 1-4 in the solid state all show apparent red light emission. Compound 4 shows sensitive luminescence quenching response to nitrobenzene (NB), and the corresponding quenching constant (K) and detection limit are 2.06 × 10 M and 9.27 ppm, respectively. This study provides a new strategy to construct CuS cluster-based coordination polymers that have great potential in various applications such as luminescence sensing.
一种六棱柱形硫化铜簇合物由于其较短的铜 - 铜键而表现出优异的近红外荧光特性，然而，构建具有扩展结构的基于硫化铜簇合物的化合物仍然是一项挑战。在此，通过巯基嘧啶衍生物与氰化铜或硫氰化铜在溶剂热条件下反应，合成了四种新的基于硫化铜簇合物的配位化合物，其化学式分别为Cu(pymt) (1)、{(CuCN)[Cu(mpymt)]} (2)、{(CuSCN)[Cu(mpymt)]} (3) 和{(CuCN)[Cu(dmpymt)]·CHCN} (4)（Hpymt = 嘧啶 - 2 - 硫醇盐，Hmpymt = 4 - 甲基 - 嘧啶 - 2 - 硫酮，Hdmpymt = 4,6 - 二甲基嘧啶 - 2 - 硫酮），并通过单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析和热重分析对其进行了表征。单晶X射线衍射分析表明，化合物1是一个零维的Cu(pymt)分子，含有一个扭曲的伪六棱柱形硫化铜核。具有同构骨架但有机连接体不同的化合物2和4呈现出一种罕见的三维骨架，具有由Cu(mpymt)单元和一维手性[Cu(CN)]链构成的nor拓扑结构；与化合物2相比，由于嘧啶配体上甲基的增加，化合物4中观察到一个更疏水的一维通道，其中乙腈分子填充在化合物4的通道中。化合物3呈现出一种由Cu(mpymt)单元和一维褶皱的(CuSCN)链构成的罕见二维层。首次通过巯基嘧啶衍生物将硫化铜簇连接到一维无机CuCN（或CuSCN）链上，从而在化合物2 - 4中获得扩展阵列。化合物1 - 4的晶体在固态下均表现出明显的红光发射。化合物4对硝基苯（NB）表现出灵敏的发光猝灭响应，相应的猝灭常数（K）和检测限分别为2.06×10 M和9.27 ppm。本研究提供了一种构建基于硫化铜簇合物的配位聚合物的新策略，该聚合物在发光传感等各种应用中具有巨大潜力。
