一种具有新颖的二重自穿插(6,8)-双节点的三维超分子网络

本文利用一个新的二羧酸配体5-羧基-1-羧甲基-2氧吡啶(H2L),合成了4个异分同构的配合物,通式为[M(HL)2(H2O)]·2H2O,M=CuII(1),ZnII(2),MnII(3),CdII(4).金属氯化物与配体H2L以1:2的摩尔比在乙醇的水溶液中混合,混合物在40～50℃下搅拌回流1小时,过滤后在室温下静置一周后,得到适合X-射线单晶衍射分析的晶体,产率为40%～50%.X-射线单晶衍射分析表明配合物1～4属异质同晶体,单斜晶系,C2/c空间群.以铜的配合物为代表进行结构分析.在最小不对称单元中包含半个CuII,一个配体HL-离子,半个配位水和一个结晶水.中心金属CuII分别与4个HL-配体的2个羧基氧原子,2个羟基氧原子和1个水分子配位,形成了一个配位数为5的近四方锥构型,其中Cu原子与4个HL-配体上的氧原子构成四方锥底面,水分子则占据锥顶位置.需要注意的是另一个羧基氧,它与金属原子之间的距离为0.2765(2)nm,根据文献可认为它与CuII之间形成了较弱的配位键,因此中心Cu原子也可以称为7配位的五角双锥构型.2个HL-配体上的羧酸氧原子和配位水分子构成五角双锥底面,另2个HL-配体上的酚羟基氧原子则占据锥顶位置.HL-配体桥联两个Cu金属中心沿a轴方向形成一维链结构,链状结构通过羧酸氧原子与配位水及结晶水分子间的氢键最终连成三维结构.从拓扑角度来看,该配合物框架是新颖的两节点(6,8)-连接的拓扑网络,其Schlfli符号为(32.45.57.6)(34.412.58.64)2.在该拓扑网络中,2个6节点和4个8节点构成四边形的螺旋通道,并且相邻的通道显示不同的螺旋结构(左旋和右旋),所以整个网络结构是外消旋的,不显手性.在这些螺旋通道中贯穿着二重菱形的自穿插结构.研究了配体H2L和配合物1～4的固相荧光光谱.配合物1的中心金属原子为Cu,发生了荧光猝灭;配合物2～4的荧光发射峰类似,在254nm的激发波长下,在483,484和515nm处分别有强的荧光发射峰,较配体的最大发射峰410nm均发生红移,表明是配体与金属之间发生了电子转移,荧光的增强可能是由于配体与金属的配位使配体的刚性增加,减少了非辐射能量的损失.     

一个新颖的(5,6)-连接三维超分子网络拓扑结构(英文)

A new complex,[Co(HL)2(H2O)4]·H2O(1)(H2L =5-carboxy-1-carboxymethyl-2-oxidopyridinium),was synthesized and characterized by X-ray single-crystal diffraction,elemental analysis,and IR spectra.The crystal is monoclinic,space group P21/c with a=0.512 69(2) nm,b=2.275 31(1) nm,c=1.003 95(6) nm,β=98.015(3)°,V= 1.159 7(1) nm3,Z=2,Mr=541.29,F(000)=558,Dc=1.550 g·cm-3,μ=0.816 mm-1,the final R=0.044 5 and wR=0.142 1 for 2 015 observed reflections(I2σ(I)).Complex 1 can be considered constructed from 2D layers,which consist of left-and right-handed helical chains and further linked into a 3D supramolecular architecture by hydrogen bonds.Topology analysis reveals that complex 1 shows an unprecedented 3D binodal(5,6)-connected topology.     

一个新的粘液酸锰(Ⅱ)配合物的合成、结构与性能研究

合成了1个以粘液酸为配体的锰(Ⅱ)配合物Mn[(muc)(H₂O)₃]·H₂O (1),并通过红外光谱,元素分析,热重分析和X-射线单晶衍射对其进行了表征。配合物1由一维链组成,其三维网络结构可以简化为dia拓扑。初步的电化学实验表明,配合物1在电化学储能上有应用潜力,可以作为氢氧化镍电极的添加剂。     

Two New Three-dimensional Supramolecular Complexes with 5-Carboxyl-1-carboxymethyl-2-oxidopyridinium: Syntheses and Crystal Structures

Two new supramolecular complexes [MnL(H2O) 4](1) and [ZnL(H2O) 5]·0.25H2O(2) (H2L = 5-carboxy-1-carboxymethyl-2-oxidopyridinium) have been synthesized and structurally characterized by elemental analysis,IR and X-ray single-crystal structure determination. Complex 1 crystallizes in the monoclinic system,space group P21/n with a = 5.1537(2) ,b = 21.2008(9) ,c = 10.9727(4) ,β = 99.182(2) °,V = 1183.54(8) 3,C8H13MnNO9,Mr = 322.13,Dc = 1.808,Z = 4,F(000) = 660,μ = 1.160,R = 0.0372 and wR = 0.0750 for 2217 observed reflections(I > 2σ(I)) . Complex 2 crystallizes in the triclinic system,space group P1 with a = 7.730(2) ,b = 8.030(2) ,c = 11.400(2) ,α = 104.27(3) ,β = 92.93(3) ,γ = 102.67(3) °,V = 664.9(2) 3,C8H15.5ZnNO10.25,Mr = 355.08,Dc = 1.774,Z = 2,F(000) = 365,μ = 1.899,R = 0.0243 and wR = 0.0695 for 2759 observed reflections(I > 2σ(I)) . Their thermal properties have been studied.