Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi, 221005, India.
Dalton Trans. 2010 Mar 14;39(10):2667-75. doi: 10.1039/b917871f. Epub 2010 Jan 20.
A series of new heterobimetallic phenylmercury(II) dithiocarbamate complexes incorporating the ferrocenyl moiety (C(5)H(5))Fe(C(5)H(4)) (Fc), namely PhHgS(2)CN(CH(2)Fc)CH(2)C(6)H(5), (1), PhHgS(2)CN(CH(2)Fc)CH(CH(3))(2), (2), PhHgS(2)CN(CH(2)Fc)(CH(2))(3)CH(3), (3) and PhHgS(2)CN(CH(2)Fc)(CH(2)C(6)H(4)CH(2)), (4) have been prepared and characterized by elemental analysis, UV-Vis, IR, (1)H and (13)C NMR spectroscopies. The crystal structures of 1, 2 and 4 showed a linear core at the Hg(II) centre of the molecule, bound by the sulfur atom of the dithiocarbamate ligand and carbon atom of the aromatic ring. Weak intermolecular Hg...S interactions form "head-to-tail" dimers in the cases of 1 and 2. 4 forms a similar dimeric structure, forming two pairs of Hg...S interactions to generate a tetrametallic unit. The observed quasi-reversible cyclic voltammograms of the complexes have been corroborated by calculating gross electron population at each atom for the neutral as well its oxidized species obtained at the density functional level (DFT) of theory, which suggests an electron withdrawing effect from the organomercury(ii)-dithiocarbamate group. The electronic absorption bands of all the four complexes were assigned with the help of time dependent density functional theory (TD-DFT) calculations. Upon excitation at approximately 440 nm 1, 3 and 4 exhibited a medium strong photoluminescence emission at approximately 500 nm as a consequence of MLCT intraligand charge transfer. 1, when excited at 256 nm exhibits photoluminescence emission at 398 nm.
一系列新的异双核苯汞(II)二硫代氨基甲酸盐配合物，其中包含二茂铁部分（C(5)H(5))Fe(C(5)H(4))(Fc)，即 PhHgS(2)CN(CH(2)Fc)CH(2)C(6)H(5)、(1)、PhHgS(2)CN(CH(2)Fc)CH(CH(3))(2)、(2)、PhHgS(2)CN(CH(2)Fc)(CH(2))(3)CH(3)和PhHgS(2)CN(CH(2)Fc)(CH(2)C(6)H(4)CH(2))、(4)已经通过元素分析、紫外可见光谱、红外光谱、(1)H 和 (13)C 核磁共振光谱进行了表征。1、2 和 4 的晶体结构显示分子中汞(II)中心的线性核心，由二硫代氨基甲酸盐配体的硫原子和芳环的碳原子结合。在 1 和 2 的情况下，弱的分子间 Hg...S 相互作用形成“头到尾”二聚体。4 形成类似的二聚体结构，形成两对 Hg...S 相互作用，生成四金属单元。观察到的配合物的准可逆循环伏安图已经通过计算中性和其在密度泛函理论(DFT)水平下获得的氧化态的每个原子的总电子密度得到证实，这表明有机汞(ii)-二硫代氨基甲酸盐基团具有电子受主效应。所有四个配合物的电子吸收带都在时间相关密度泛函理论(TD-DFT)计算的帮助下进行了分配。在大约 440nm 的激发下，1、3 和 4 在大约 500nm 处表现出中等强度的光致发光发射，这是由于 MLCT 内配位体电荷转移所致。当 1 在 256nm 激发时，在 398nm 处表现出光致发光发射。
