一维链状1,8-萘二酸四核锌配位聚合物[Zn4(1,8-nap)4(4,4''-bipy)2·0.5en·H2O]n的合成、结构、热稳定性及发光性质

羧酸配位聚合物是金属离子与有机羧酸构造块通过配位键或其他分子间弱作用力经自组装而成的一维、二维、三维的聚合物.由于这些配位聚合物具有新颖的拓扑结构以及在功能材料方面的潜在应用,同时又由于羧酸配合物比较稳定,所以设计和调控特殊配位聚合物成了当前的研究热点[1～4].     

4-甲基苯硫乙酸与含氮配体构筑的两个化合物的合成，晶体结构，热稳定性与发光性质的研究

合成了2个配合物[ZnL₂(Him)₂] (1)和[ (Cu₂L₂(phen)₂( μ₂-Cl)₂)·(Cu₂( μ₂-L)₂(phen)₂Cl₂)] (2)(L=4-甲基苯硫乙酸,Him=咪唑,phen=1,10-邻菲咯啉),进行了元素分析、红外、热重等表征,并测定了其晶体结构。配合物1晶体属于单斜晶系,空间群为C2/c。配合物2晶体属于三斜晶系,空间群为P1。配合物1是由N-H…O氢键作用形成的一维带状结构。配合物2的单胞中含有2个分别由氯原子与羧基氧原子桥联的双核独立分子,通过C-H…O,C-H…Cl氢键以及C-H…π作用而构成三维结构。室温固体荧光分析显示配合物1具有较强荧光吸收。     

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.     

一维链状1，8-萘二酸四核锌配位聚合物[Zn4(1，8-nap)4(4，4′-bipy)2·0.5en·H2O]n的合成、结构、热稳定性及发光性质

A coordination polymer [Zn₄(1，8-nap)₄(4，4′-bipy)₂·0.5en·H₂O]_n (where 1，8-nap is 1，8-naphthalenedi-carboxylate， 4，4′-bipy is 4，4′-bipyridine and en is ethylenediamine) has been hydrothermally synthesized and characterized by elemental analysis， IR， TG and single crystal X-ray diffraction. The title complex belongs to triclinic system with space group P1， a=1.026 94(2) nm， b=1.134 52(2) nm， c=1.348 64(3) nm， α=79.992°， β=73.838°， γ=84.246°， V=1.484 nm³， Z=1， M_r=1 478.59， D_c=1.655 g·cm^-3， R=0.031 8， wR=0.087 6. The crystal structure of title complex shows that four 1，8-naphthalenedicarboxylate ligands coordinate with zinc atoms to form tetranuclear units which are further connected via 4，4′-bipy ligands to generate 1D double-chain structure. The luminescent property of the complex is also studied in this paper. CCDC: 657266.     

Crystal Structure of catena-[（Tetrakis-μ2-acetato-μ2-4,4＇-bipyridine） dicopper（Ⅱ）] Acetonitrile Solvate

1 INTRODUCTION Much attention has been paid to 1D, 2D and 3D coordination polymers because they can meet the need of functional materials with desired structures and properties[1～5]. One strategy in the design and synthesis of coordination architectures is the buil- ding-block approach. Commonly, bi- or multidentate organic ligands containing N[6, 7] or O[8, 9] atoms have ever been used in the construction. In our cur- rent work, we have selected melamine ligand as the main building bl…     

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.     

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.