3-(4′-羧基-苯氧基)苯甲酸构筑的Cu(Ⅱ)/Zn(Ⅱ)配位聚合物的合成、晶体结构及对丙酮和Tb^(3+)离子的荧光传感

Cu(Ⅱ)/Zn(Ⅱ)Coordination Polymers Constructed by 3-(4′-Carboxy-phenoxy)benzoic Acid:Synthesis,Crystal Structure and as a Fluorescence Sensor to Acetone and Tb^(3+)Ion

利用水热法合成了2个新的配位聚合物(CPs):[M(3,4′-oba)(phen)(H2O)]n(M=Zn(1)、Cu(2),3,4′-H2oba=3-(4′-羧基-苯氧基)苯甲酸,phen=菲咯啉),并用X射线单晶衍射测定其晶体结构。CP 1为一维链状结构,中心金属Zn^(2+)的配位环境为[ZnO_(3)N_(2)],形成四方锥构型。配体3,4′-oba以μ_(1)∶η^(1)η^(0)/μ_(1)∶η^(1)η^(0)的模式与Zn^(2+)配位。CP 2中Cu^(2+)的配位环境为[CuO_(4)N_(2)],呈扭曲的八面体构型。配体3,4′-oba采用μ_(1)∶η^(1)η^(0)/μ_(1)∶η^(1)η^(1)的模式连接2个Cu^(2+)形成一维“之”字链结构。一维链分别通过分子间氢键C—H…O(1)和O—H…O(2)形成二维超分子网状结构。配体phen以双齿螯合的形式与Zn^(2+)/Cu^(2+)配位。CP 1表现出强的荧光,归因于配体的π*-π跃迁。研究了1在不同溶剂中的发光性能以及对镧系金属离子的荧光敏化效果。CP 1的荧光被丙酮分子猝灭,而可以敏化稀土金属Tb^(3+)离子发出强的绿色荧光,因而1可作为检测丙酮分子和Tb^(3+)离子的荧光传感器。

Taking 3-(4′-carboxyl-phenyloxy)benzoic acid(3,4′-H2oba)and phenanthroline(phen)as ligands,two coordination polymers(CPs)[M(3,4′-oba)(phen)(H2O)]n(M=Zn(1),Cu(2))were synthesized by hydrothermal method and their structures were characterized by X-ray single crystal diffraction.CP 1 features a one-dimensional chain structure.The coordination environment of Zn^(2+)ion is[ZnO_(3)N_(2)],forming tetragonal vertebral configuration.The Zn^(2+)ions are linked by 3,4′-oba ligands throughμ_(1)∶η^(1)η^(0)/μ_(1)∶η^(1)η^(0) coordination modes.CP 2 has a structure with[CuO_(4)N_(2)]coordination unit.Ligand 3,4′-oba uses the pattern ofμ_(1)∶η^(1)η^(0)/μ_(1)∶η^(1)η^(1) to connect two Cu^(2+)to form a 1D zigzag chain structure.The 1D chain forms a 2D supramolecular network structure through hydrogen bonds(C—H…O in 1 and O—H…O in 2).Ligand phen coordinates with Zn^(2+)/Cu^(2+)by bidentate chelation mode.CP 1 showed strong fluorescence,which is attributed to theπ*-πtransition of the ligand.The fluorescence properties of 1 in different solvents and the fluorescence sensitization effect on lanthanide metal ion were studied.The fluorescence of CP 1 was quenched by acetone molecule,and it can sensitize the rare earth metal Tb^(3+)ions to emit strong green fluorescence.Therefore,1 can be used as a fluorescence sensor for detecting acetone molecule and Tb^(3+)ion.CCDC:2005286,1;2005285,2.