Influence of the ligand frameworks on the coordination environment and properties of new phenylmercury(II) beta-oxodithioester complexes

Rajput Gunjan; Yadav Manoj Kumar; Drew Michael G. B.; Singh Nanhai

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Influence of the ligand frameworks on the coordination environment and properties of new phenylmercury(II) beta-oxodithioester complexes

机译：配体构架对新的苯基汞（II）β-氧二硫酯配合物配位环境和性能的影响

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New phenylmercury(II) complexes of the form [PhHg(L1), PhHg(L2) and PhHg(L3)] (L1 = methyl-3-hydroxy- 3-(p-methoxyphenyl)-2-propenedithioate (1), L2 = methyl-3-hydroxy-3-(p-bromophenyl)-2-propenedithioate (2) and L3 = methyl-3-hydroxy-(3-pyridyl)-2-propenedithioate (3)) have been synthesized and characterized by elemental analysis, IR, UV-Vis, H-1 and C-13 NMR. The crystal structures of 1-3 reveal a linear geometry about the mercury atom via ipso-C and S11 atoms. 1 and 2 exhibited O, S-coordination whereas 3 preferred S, S-coordination. Intramolecular Hg...O bonding interactions are also observed in 1 and 2 at distances of 2.638(14), 2.644(10) angstrom respectively. However in 3, incorporation of the 3-pyridyl substituent on the ligand enhanced the proximity of S13 and N14, giving rise to significant intramolecular Hg...S and intermolecular Hg...N interactions at 3.141(5) angstrom and 2.77(2) angstrom respectively generating a 1-D polymeric chain motif. The O,S- or S, S-coordination preference and Hg...N interactions have been assessed by DFT calculations. All the complexes show metal perturbed ligand-centred luminescence characteristics in solution and in the solid phase. The band gap values 2.54, 2.66 and 2.61 eV for 1, 2 and 3, respectively, evaluated from the diffuse reflectance spectroscopy show the semiconducting nature of the complexes.

机译：[PhHg（L1），PhHg（L2）和PhHg（L3）]形式的新苯基汞（II）配合物（L1 =甲基-3-羟基-3-（对甲氧基苯基）-2-丙二硫代乙酸酯（1），L2 =合成了3-羟基-3-（对溴苯基）-2-丙二硫代酸甲酯（2）和L3 =合成了3-羟基-（3-吡啶基）-2-丙二硫代酸甲酯（3）），并用元素分析，IR，UV-Vis，H-1和C-13 NMR。 1-3的晶体结构通过ipso-C和S11原子揭示了围绕汞原子的线性几何结构。 1和2显示出O，S配位，而3显示出优选的S，S配位。在1和2中分别在2.638（14）和2.644（10）埃的距离处观察到分子内Hg ... O键相互作用。然而，在3中，在配体上并入3-吡啶基取代基增强了S13和N14的接近性，从而在3.141（5）埃和2.77（2）处产生了显着的分子内Hg ... S和分子间Hg ... N相互作用。埃分别产生一维聚合物链基序。 O，S或S，S配位偏好和Hg ... N相互作用已通过DFT计算进行了评估。所有的配合物在溶液和固相中都表现出金属干扰以配体为中心的发光特性。根据漫反射光谱法评估的1、2和3的带隙值分别为2.54、2.66和2.61 eV，显示了配合物的半导体性质。

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《Dalton transactions: An international journal of inorganic chemistry》 |2015年第12期|共8页
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Rajput Gunjan; Yadav Manoj Kumar; Drew Michael G. B.; Singh Nanhai;
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Influence of the ligand frameworks on the coordination environment and properties of new phenylmercury(II) beta-oxodithioester complexes

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