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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Photophysical, electrochemical and TD-DFT studies of Ni(II) and Mn(II) complexes of N '-(2-methylfuran-3-carbonyl)hydrazine carbodithioic acid ethyl ester
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Photophysical, electrochemical and TD-DFT studies of Ni(II) and Mn(II) complexes of N '-(2-methylfuran-3-carbonyl)hydrazine carbodithioic acid ethyl ester

机译：Ni（II）和N' - （2-甲基呋喃-3-羰基）肼碳酸乙酯的Ni（II）和Mn（II）配合物的光药，电化学和TD-DFT研究

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摘要

Two new complexes [Ni(Hmfchce)(2)(PY)(2)] (1) and [Mn(limfchce)(2)(o-phen)] (2) with [N'-(2-methylfuran-3-carbonyl)hydrazine]-carbodithioic acid ethyl ester (H(2)mfchce) have been synthesized which contain o-phenanthroline (o-phen)/pyridine (py) as coligand. The ligand and its metal complexes have been characterized by elemental analyses. IR, magnetic susceptibility and single crystal X-ray diffraction data. Complexes 1 and 2 crystallize in orthorhombhic system with space group 'Pbca' and 'Pbcn', respectively. In complex 1, nickel centre is coordinated through one hydrazine nitrogen atom, one carbonyl oxygen of two units of ligand and two pyridine nitrogen atoms. The manganese center in complex 2 is coordinated in a N4O2 core by two uininegative bidentate ligands using hydrazine nitrogen (after loss of proton) and carbonyl oxygen and two nitrogen atoms of o-phen. In both complexes, the metal ion adopts a distorted octahedral geometry. Complexes 1 and 2 are fluorescent materials which exhibit an emission at 291 and 285 nm, respectively upon excitation at 263 and 251 nm. The course of the thermal degradations of complexes 1 and 2 have been investigated by TGA which indicate that metal oxide is formed as the final residue in both complexes. The metal complexes, [Ni(Hmfchce)(2)(Py)(2)] (1) and [Mn(Hmfchce)2(o-phen)] (2) were immobilized on glassy carbon electrodes using Nafion (R) (NO. The modified electrodes have been characterized by cyclic voltammetry in 0.1 M KOH. Complexes 1 and 2 have efficient activity towards electrochemical water oxidation in the 0.1 M KOH. The simulated spectra of the two complexes 1 and 2 are characterized by excited states with ligand-to-ligand charge-transfer (LLCT) and ligand-to-metal charge-transfer (LMCT) character. (C) 2019 Elsevier Ltd. All rights reserved.
机译：两种新配合物[Ni（HMFCHCE）（2）（2）（Py）（2）]（1）和[Mn（Limfchce）（2）（2）（O-Phen）]（2）与[n' - （2-甲基呋喃-3 - 碳羰基]碳氢氧化钛酸乙酯（H（2）MFCHCE）已合成，其含有邻菲咯啉（O-Phen）/吡啶（Py）作为Coligand。用元素分析表征配体及其金属配合物。 IR，磁化率和单晶X射线衍射数据。复合物1和2分别在与空间组'PBCA'和“PBCN”中的正交系统中结晶。在络合物1中，镍中心通过一个肼氮原子配位，两个配体的一个羰基氧和两个吡啶氮原子。复合物2中的锰中心通过使用肼氮（在质子丧失后的含有肼）和羰基氧和O-Phen的两个氮原子中，在N4O2核心中配位。在两个复合物中，金属离子采用扭曲的八面体几何形状。复合物1和2是在263和251nm的激发时分别在291和285nm处表现出在291和285nm处的发射的荧光材料。通过TGA研究了复合物1和2的热降解的过程，所述TGA表明金属氧化物形成为两个配合物中的最终残留物。金属配合物，[Ni（HMFCHCE）（2）（2）（2）（2）（2）]（1）和[Mn（HMFCHCE）2（O-Phen）]（2）固定在玻璃碳电极上使用Nafion（R）（不。通过循环伏安法在0.1M KOH中表征了改性电极。复合物1和2在0.1M KOH中具有有效的电化学水氧化活性。两个配合物1和2的模拟光谱的特征在于具有配体的激发态-to-pigand电荷 - 转移（L1ct）和配体 - 金属电荷转移（LMCT）特征。（c）2019 Elsevier Ltd.保留所有权利。

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