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基于炔基-亚氨基吡啶的三核镍(II)、锌(II)、镉(II)和铜(II)配合物:结构、电化学、发光及非线性光学性质

Alkynyl-Iminopyridine-Based Trinuclear Ni(II), Zn(II), Cd(II), and Cu(II) Complexes: Structural, Electrochemical, Luminescence and Nonlinear Optical Properties.

作者信息

Naiknaware Namita H, Deshmukh Ajit H, Patil Ashwini S, Chavan Sanjay S

机构信息

Department of Chemistry, Shivaji University, Kolhapur, MS, 416 004, India.

出版信息

J Fluoresc. 2025 Jun 2. doi: 10.1007/s10895-025-04381-0.

Abstract

A new series of alkynyl-functionalized trinuclear metal complexes, with the general formula [M₃(L/L)(Cl)₆] (M = Ni(II), Zn(II), Cd(II), Cu(II)), were synthesized using alkynyl-functionalized iminopyridine ligands L and L. The complexes were characterized by various techniques, including FTIR, NMR, ESI-MS, UV-Vis, ESR, TGA, PXRD, and SEM. All synthesized complexes exhibit absorption in the visible region, primarily attributed to metal-to-ligand charge transfer (MLCT) and intra-ligand charge transfer (ILCT) transitions. Electrochemical investigations of the Ni(II) and Cu(II) analogues reveal quasireversible redox behavior. EPR spectral analysis of the Cu(II) complexes indicates a significant degree of covalency in the metal-ligand interactions. All complexes emit red luminescence at room temperature. The second harmonic generation (SHG) efficiency, evaluated via the Kurtz powder technique, highlights the potential of these complexes as promising candidates for nonlinear optical (NLO) applications.

摘要

利用炔基功能化的亚氨基吡啶配体L和L合成了一系列通式为[M₃(L/L)(Cl)₆](M = Ni(II)、Zn(II)、Cd(II)、Cu(II))的新型炔基功能化三核金属配合物。通过多种技术对这些配合物进行了表征,包括傅里叶变换红外光谱(FTIR)、核磁共振(NMR)、电喷雾电离质谱(ESI-MS)、紫外可见光谱(UV-Vis)、电子顺磁共振(ESR)、热重分析(TGA)、粉末X射线衍射(PXRD)和扫描电子显微镜(SEM)。所有合成的配合物在可见光区域均有吸收,主要归因于金属到配体的电荷转移(MLCT)和配体内电荷转移(ILCT)跃迁。对Ni(II)和Cu(II)类似物的电化学研究揭示了准可逆的氧化还原行为。对Cu(II)配合物的电子顺磁共振光谱分析表明,金属-配体相互作用中存在显著程度的共价性。所有配合物在室温下均发出红色荧光。通过库尔茨粉末技术评估的二次谐波产生(SHG)效率突出了这些配合物作为非线性光学(NLO)应用的有前景候选物的潜力。

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