Naeem Nafeesa, Mughal Ehsan Ullah, Bozkurt Ebru, Ahmed Ishtiaq, Zafar Muhammad Naveed, Ayub Ali Raza, Sadiq Amina, Alsimaree Abdulrahman A, Alsantali Reem I, Ahmed Saleh A
Department of Chemistry, University of Gujrat Gujrat-50700 Pakistan
Program of Occupational Health and Safety, Vocational College of Technical Sciences, Atatürk University 25240 Erzurum Turkey.
RSC Adv. 2025 Apr 7;15(14):10825-10850. doi: 10.1039/d5ra01005e. eCollection 2025 Apr 4.
This manuscript provides a comprehensive overview of the synthesis, characterization, and photophysical and electrochemical properties of terpyridine-based metal complexes (C-C). The synthesis of these terpyridine (TPY) complexes involves the coordination of TPY ligands (L-L) with transition metal ions, leading to a variety of novel structural and electronic configurations. The characterization of TPY ligands and their complexes is carried out using various techniques, including UV-Vis spectroscopy, NMR, FTIR and mass spectrometry. To the best of our knowledge, for the first time, we comprehensively investigate the photophysical, solvatochromic, electrochemical, and computational properties of an extensive series of TPY-based metal complexes (C-C) within a single framework. The solvatochromic behavior of the synthesized complexes (C-C) is explored, revealing their sensitivity to solvent polarity, which is a key factor influencing their photophysical properties. The TPY-based complexes (C-C) exhibited solvent-dependent fluorescence behavior, with distinct ILCT and MLCT mechanisms, and enhanced fluorescence in specific solvents, particularly for Zn(ii) and Cu(ii) complexes. The absorption and emission characteristics of the complexes are studied in dilute solutions to explore their structure-property relationships. Additionally, the electrochemical properties of the TPY-based metal complexes (C-C) are investigated, highlighting their redox activity and potential for use in energy storage and conversion applications. Density functional theory (DFT) calculations are employed to provide detailed insights into the electronic structure and reactivity of these complexes, supporting the experimental observations. The correlation of electronic band gaps with photophysical and electrochemical behaviors showed compounds as promising candidates with efficient charge transfer and strong fluorescence. The integrated analyses reveal the exceptional potential of this scaffold for advanced materials applications, highlighting its versatility and significance in cutting-edge research.
本手稿全面概述了基于三联吡啶的金属配合物（C-C）的合成、表征以及光物理和电化学性质。这些三联吡啶（TPY）配合物的合成涉及TPY配体（L-L）与过渡金属离子的配位，从而产生各种新颖的结构和电子构型。使用包括紫外-可见光谱、核磁共振、傅里叶变换红外光谱和质谱等各种技术对TPY配体及其配合物进行表征。据我们所知，我们首次在单一框架内全面研究了一系列广泛的基于TPY的金属配合物（C-C）的光物理、溶剂致变色、电化学和计算性质。研究了合成配合物（C-C）的溶剂致变色行为，揭示了它们对溶剂极性的敏感性，而溶剂极性是影响其光物理性质的关键因素。基于TPY的配合物（C-C）表现出溶剂依赖性荧光行为，具有独特的分子内电荷转移（ILCT）和金属到配体电荷转移（MLCT）机制，并且在特定溶剂中荧光增强，特别是对于锌（II）和铜（II）配合物。在稀溶液中研究了配合物的吸收和发射特性，以探索它们的结构-性质关系。此外，还研究了基于TPY的金属配合物（C-C）的电化学性质，突出了它们的氧化还原活性以及在能量存储和转换应用中的潜力。采用密度泛函理论（DFT）计算来深入了解这些配合物的电子结构和反应性，支持实验观察结果。电子带隙与光物理和电化学行为的相关性表明，这些化合物是具有有效电荷转移和强荧光的有前途的候选物。综合分析揭示了该支架在先进材料应用中的特殊潜力，突出了其在前沿研究中的多功能性和重要性。
