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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu2I2)(n) (n=2, 3) in their coordination polymers
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Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu2I2)(n) (n=2, 3) in their coordination polymers

机译：二硫醚间隔基的刚性对其配位聚合物中发光簇（Cu2I2）（n）（n = 2，3）的大小的影响

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摘要

Treatment of CuI with the flexible PhS(CH2)(4)SPh dithioether ligand in MeCN solution affords the strongly luminescent metal-organic 2D coordination polymer [Cu4I4{mu-PhS(CH2)(4)SPh}(2)](n) (1). The interpenetrated 2D network of 1 is built upon by Cu-4(mu(3)-I)(4) cubane-like clusters as secondary building units (SBUs), which are interconnected via bridging 1,4-bis(phenylthio) butane ligands. In contrast, the auto-assembly reaction of the unsaturated semi-flexible PhSCH2C CCH2SPh ligand with CuI results in formation of the 3D metallopolymer [(Cu6I6){mu-PhSCH2C CCH2SPh}(3)](n) (2). The SBUs of luminescent 2 consist of discrete Cu-6(mu(3)-I)(6) hexagon prisms, which are coordinated with bridging 1,4-bis(phenythio) butyne ligands via Cu-S bonds. Contrary to the other rare literature-known examples of metallopolymers incorporating Cu6X6 SBUs as connecting nodes, the Cu center dot center dot center dot Cu interactions of 2 [2.8484(6)angstrom] are markedly shorter, being close to the sum of the Van der Waals radii of two Cu atoms (similar to 2.8 angstrom). The photophysics of these compounds, which exhibit reversible luminescence thermochromism, has been investigated in detail. The solid-state luminescence spectra of 1 and 2 feature at room temperature intense emissions around 560 and 555 nm, respectively. The luminescence properties of the unusual Cu-6(mu(3)-I)(6) hexagon prism motif are rationalized by means of DFT and TDDFT computations.
机译：在MeCN溶液中用柔性PhS（CH2）（4）SPh二硫醚配体处理CuI，可得到强发光的金属有机二维配位聚合物[Cu4I4 {mu-PhS（CH2）（4）SPh}（2）]（n） （1）。 1的互穿2D网络是由Cu-4（mu（3）-I）（4）古巴式簇作为二级建筑单元（SBU）建立的，它们通过桥接1,4-双（苯硫基）丁烷相互连接配体。相反，不饱和半柔性PhSCH2C CCH2SPh配体与CuI的自组装反应导致形成3D金属聚合物[（Cu6I6）{mu-PhSCH2C CCH2SPh}（3）]（n）（2）。发光2的SBU由离散的Cu-6（mu（3）-I）（6）六角棱镜组成，这些棱镜与通过Cu-S键桥接的1,4-双（苯硫基）丁炔配体配合使用。与结合Cu6X6 SBU作为连接节点的金属聚合物的其他稀有文献已知的实例相反，Cu中心点中心点中心点Cu相互作用为2 [2.8484（6）埃]明显更短，接近Van der之和两个铜原子的华氏半径（约2.8埃）。这些化合物的光物理表现出可逆的发光热致变色现象，已被详细研究。室温下1和2的固态发光光谱分别具有大约560 nm和555 nm的强发射。通过DFT和TDDFT计算合理化了不寻常的Cu-6（mu（3）-I）（6）六边形棱镜图案的发光特性。

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