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基于2-(2-羧基苯基)咪唑并(4,5-)-(1,10)菲咯啉配体的六种镧系元素配合物的合成、结构与性质

Synthesis, structures and properties of six lanthanide complexes based on a 2-(2-carboxyphenyl)imidazo(4,5-)-(1,10)phenanthroline ligand.

作者信息

Ren Shanshan, Jiang Wei, Wang Qingwei, Li Zhimin, Qiao Yu, Che Guangbo

机构信息

Key Laboratory of Preparation and Application of Environmental Friendly Materials (Jilin Normal University), Ministry of Education Changchun 130103 P. R. China

College of Chemistry, Jilin Normal University Siping 136000 China.

出版信息

RSC Adv. 2019 Jan 22;9(6):3102-3112. doi: 10.1039/c8ra09207a.

DOI:10.1039/c8ra09207a
PMID:35518952
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9059995/
Abstract

Six lanthanide complexes [Tb(2-NCP)(NO)] (1), [Eu(2-NCP)(3-PYC)] (2), [Sm(2-NCP)(3-PYC)] (3), [Eu(2-NCP)(SA)] (4), [Tb(2-NCP)(SA)] (5) and [Tb(2-NCP)(AA)] (6) (2-HNCP = 2-(2-carboxyphenyl)imidazo(4,5-)-(1,10)phenanthroline, 3-HPYC = pyridine-3-carboxylic acid, HSA = succinic acid, HAA = adipic acid) have been synthesized by hydrothermal route, and the crystal structures were analyzed through elemental analysis, infrared spectroscopy, single crystal X-ray diffraction. Complexes 1 and 6 present two-dimensional (2D) layers, which are further connected to three-dimensional (3D) supramolecular architectures through C-H⋯π interactions. Complexes 2 and 3 exhibit infinite one-dimensional chains. Finally, the neighboring chains are packed by C-H⋯π interactions, giving rise to 3D supramolecular network. Complexes 4 and 5 display 2D layers, which are further extend to 3D supramolecular structures C-H⋯O intermolecular hydrogen bonding. Six complexes possess good thermal stabilities, characteristic photoluminescence properties, and photocatalytic activities for the degradation of organic dyes under visible light irradiation. In addition, the complex 6 exhibits significantly enhanced photocatalytic activity for methylene blue, and the degradation rate could reach 81.2% in 370 min. Meanwhile trapping experiments indicated that the hole, ·O and ·OH are the main activated species. Furthermore, by comparing the photoluminescent and photocatalytic mutation results of same metal complexes induced by interconversion of coligands, we confirm that the properties mutation induced by coligands is much obvious and controllable.

摘要

通过水热法合成了六种镧系配合物[Tb(2-NCP)(NO)] (1)、[Eu(2-NCP)(3-PYC)] (2)、[Sm(2-NCP)(3-PYC)] (3)、[Eu(2-NCP)(SA)] (4)、[Tb(2-NCP)(SA)] (5)和[Tb(2-NCP)(AA)] (6)(2-HNCP = 2-(2-羧基苯基)咪唑并(4,5-)-(1,10)菲啰啉,3-HPYC = 吡啶-3-羧酸,HSA = 琥珀酸,HAA = 己二酸),并通过元素分析、红外光谱、单晶X射线衍射对晶体结构进行了分析。配合物1和6呈现二维(2D)层,通过C-H⋯π相互作用进一步连接成三维(3D)超分子结构。配合物2和3呈现无限一维链。最后,相邻链通过C-H⋯π相互作用堆积,形成3D超分子网络。配合物4和5呈现二维层,通过C-H⋯O分子间氢键进一步扩展为3D超分子结构。六种配合物具有良好的热稳定性、特征光致发光性能以及在可见光照射下对有机染料的光催化降解活性。此外,配合物6对亚甲基蓝表现出显著增强的光催化活性,在370分钟内降解率可达81.2%。同时,捕获实验表明空穴、·O 和·OH是主要的活性物种。此外,通过比较配体相互转化诱导的相同金属配合物的光致发光和光催化突变结果,我们证实配体诱导的性质突变更加明显且可控。

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