基于构象灵活的N-杂环配体构筑的3D拟卤化亚铜配合物的合成、结构和性质研究  

Synthesis,Structure and Properties of 3D Copper (Ⅰ) Pseudohalide Compound Constructed by Conformationally Flexible N-Heterocylic Ligand

作　　者：秦英恋 秦建芳[1] QIN Yinglian;QIN Jianfang(Department of Applied Chemistry, Yuncheng University, Yuncheng 044000, China)

机构地区：[1]运城学院应用化学系,运城044000

出　　处：《人工晶体学报》2022年第6期1059-1068,共10页Journal of Synthetic Crystals

基　　金：山西省高等学校科技创新项目(2021L475);运城学院应用研究项目(CY-2020017,CY-2021012);山西省重点学科建设经费资助(FSKSC);运城学院大学生创新创业训练项目(DC2022)。

摘　　要：溶剂热条件下,通过无机阶梯状链[Cu(SCN)]_(n)与柔性有机配体1,3-二(4-吡啶基)丙烷(bpp)自组装,得到了一例新型的3D有机-无机杂化配合物[Cu_(4)(SCN)_(4)(bpp)_(2)]_(n)(1)。值得关注的是,不对称单元中的bpp配体显示两种不同的构象(trans-gauche或trans-trans),并连接梯形的[Cu(SCN)]_(n)链形成结晶学独立的[Cu_(2)(SCN)_(2)(bpp)]_(n)(A和B)层。紧接着,两个不同的层通过ABB′A′的顺序排列形成独特的三维褶皱结构。进一步对配合物1进行了红外光谱(FT-IR)、粉末衍射(PXRD)、热分析、固体紫外-可见漫反射光谱(UV-Vis)和光致发光性质研究。固体紫外-可见光谱表明配合物在紫外区有强的吸收并且具有半导体性质,带隙能E_(g)为3.20 eV。光催化性能测试结果表明,配合物1在紫外光照射下对中性红(NR)、甲基橙(MO)、天青I(AI)、亚甲基蓝(MB)和亮蓝(ED)这五种染料表现出不同的光催化活性,这可能与有机染料的尺寸和电荷差异有关。此外,荧光测试表明配合物在室温下表现出较强的绿色发光性质,在525 nm附近有强的荧光发射峰。这种发射可能与配体中心激发态有关,可能涉及金属到配体或配体到配体的电荷转移。A new 3D organic-inorganic hybrid solid[Cu_(4)(SCN)_(4)(bpp)_(2)]_(n)(1)was obtained via the self-assembly of inorganic ladder-like chains[Cu(SCN)]_(n) with the flexible organic ligands 1,3-di(4-pyridyl)propane(bpp)under solvothermal conditions.It is noted that the bpp ligands show two kinds of conformations(trans-gauche or trans-trans)in the asymmetric unit,which linked by similar staircase-like[Cu(SCN)]_(n) chains to form crystallographically distinct[Cu_(2)(SCN)_(2)(bpp)]_(n) layers A and B.Furthermore,two different layers are packed in an offset ABB′A′pattern to generate unique 3D structure.Compound 1 was further characterized by infrared spectroscopy(FT-IR),powder diffraction(PXRD),thermal analysis,solid state diffuse reflectance spectroscopy(UV-Vis)and photoluminescent studies.The solid UV-Vis diffuse-reflectance spectroscopy shows strong absorption spectra in ultraviolet region,and a wide-gap semiconductor with band gap of 3.20 eV.Compound 1 shows different photocatalytic activities for neutral red(NR),methyl orange(MO),azure I(AI),methylene blue(MB)and brilliant blue(ED)degradation under UV-light irradiation,which could be related to the slight charge and size difference of organic dyes.Compound 1 shows strong green photoluminescence at room temperatures with emission peaks at about 525 nm,which may be associated with a ligand-centered excited state with a possible involvement of metal-to-ligand or ligand-to-ligand charge transfer.

关 键 词：自组装 有机-无机杂化 拟卤化亚铜配合物 柔性桥联配体 晶体结构 发光性能 光催化性能 

分 类 号：O641[理学—物理化学]