Syntheses,Structures and Luminescent Properties of Zinc(II) and Cadmium(II) Complexes With the Ditopic Ligand 1,3-Bis(imidazol-1-ylmethyl)benzene

Abstract  

Three new complexes, namely [Zn(mbix)(SO₄)]·CH₃OH (1), Cd(mbix)₂(NO₃)₂ (2) and [Cd(mbix)₂(H₂O)₂]·(NO₃)₂ (3), have been obtained by reactions of flexible bidentate ligand 1,3-bis(imidazol-1-ylmethyl)benzene (mbix) with corresponding zinc(II) and cadmium(II) salts. The structures of these complexes have been determined by the X-ray single crystal diffraction analysis. Complex 1 features a 2D wavy network with (4,4) topology. Complex 2 has a 2D grid network with left- and right-handed helical chains, while complex 3 exhibits twofold parallel interpenetration structure. The differences of three complexes demonstrate that the coordination geometry of metal ions and the ratio of reactants have a great impact on the structure of the supramolecular architectures. The luminescent properties of three complexes are also investigated.     

以芳香羧酸及双咪唑基化合物为配体的钴配合物的合成和晶体结构

以硝酸钴、4,4’-（六氟异丙基）二（苯甲酸）（H₂FBA）和1,2-二咪唑基二甲苯（OBIX）或4,4’-二咪唑基二甲联苯（BIMB）为原料,在水热条件下得到2个结构不同的配位聚合物[Co（OBIX）（FBA）]_n（1）和[Co₂（BIMB）₂（FBA）₂]_n（2）。对它们进行了元素分析、红外光谱分析,并利用X-射线衍射测定了它们的单晶结构。配合物1中2个钴离子通过2个OBIX配体桥连成一个24元大环,它再通过FBA配体连接成一维管状结构,而配合物2中钴离子通过两种配体连接成一维左右两种螺旋结构,2种螺旋结构通过交替互锁形成二维层状结构。结果说明了辅助配体在配合物组装过程中起着非常重要的作用。     

Syntheses, structures, and magnetic properties of new rare earth coordination polymers constructed by 1,3,5-benzenetriacetic acid

Three new coordination polymers with formula [Gd(bta)(H₂O)·1.39H₂O] _n (1), [Dy(bta)(H₂O)·1.35H₂O] _n (2) and [Y(bta)(H₂O)₂·0.5H₂O] _n (3) were synthesized by using corresponding rare earth nitrates and 1,3,5-benzenetriacetic acid (H₃bta) under hydrothermal/solvothermal reaction conditions, and characterized by single-crystal X-ray diffraction. In these complexes, the carboxylate groups of bta³⁻ adopt different coordination modes, namely one carboxylate group adopts μ₂-η¹:η¹-bridging and each of the other two carboxylate groups adopts μ₂-η²:η¹-bridging coordination modes in 1 and 2, and one carboxylate group adopts a μ₂-η²:η¹-bridging coordination mode and each of the other two carboxylate groups adopts a μ₂-η¹:η¹-bridging mode for the major component and one carboxylate group adopts a μ₂-η²:η¹-bridging coordination mode, one has a μ₂-η¹:η¹-bridging mode and the third has a monodentate mode for the minor component in 3. The magnetic properties of the complexes 1 and 2 were investigated in the temperature range of 1.8–300 K.     

新型配位聚合物[Zn6(bta)4(2,2''''-bipy)3 ]的合成、晶体结构和荧光性质

采用水热法合成了一种新的三维配位聚合物[Zn6(bta)4(2,2'-bipy)3](H3bta=1,3,5-苯三乙酸; 2,2'-bipy=2,2'-二联吡啶), 并通过X 射线单晶结构分析、红外光谱、元素分析和热重分析对该配合物进行了表征. 结构分析数据表明, 该配合物属单斜晶系, Cc空间群, 晶胞参数a=1.7714(4) nm, b=2.4391(5) nm, c=1.7120(3) nm, β=104.39(3)°, Z=4, V=7.165(2) nm3, Dc=1.722 g/cm3, μ=2.065 mm-1, F(000)=3768, R1=0.0645, wR2=0.1424. 荧光光谱结果表明, 配合物具有良好的荧光性质.     

基于PbBr2的有机-无机杂化化合物的合成和晶体结构

合成得到了2个新的有机-无机杂化化合物{（4-CH₃-Bz-4-Ph-Py）[PbBr₃]}_n（1）（4-CH₃-Bz-4-Ph-Py⁺=4-甲基苄基-4-苯基吡啶离子）和{（4-F-Bz-4-Ph-Py）[PbBr₃]}_n（2）（4-F-Bz-4-Ph-Py⁺=4-氟苄基-4-苯基吡啶离子）。对化合物1和2进行了元素分析、粉末X射线衍射等表征,并利用X射线单晶衍射测定了它们的单晶结构,配合物1与2同构,均属于正交晶系,P2₁2₁2空间群。结构研究表明,配合物1和2中,铅溴八面体通过共边连接方式,形成[Pb₃Br₉]_n三链,有机阳离子填充在无机溴化铅链空隙中。配合物1和2均未作手性分离。     

三核锌配合物的合成及结构表征

A trinuclear Zn(Ⅱ) complex [Zn₃(L)₂(Cl)₂(OSO₃)₂(H₂O)₂]·2H₂O (1) (L=N¹-(2-aminoethyl)-N¹-(2-imidazolethyl)-ethane-1,2-diamine) was synthesized by reaction of ligand L with ZnSO₄·7H₂O at pH=9 in air. The complex has been characterized by elemental analysis, FTIR and X-ray single crystal diffraction. It reveals that the crystal of complex 1 belongs to monoclinic C2/c space group, a=3.516 9(7) nm, b=0.676 57(14) nm, c=1.502 2(3) nm, β=110.955(4)°, V=3.337 9(12) nm³, Z=4. In complex 1, two ligands L bridge three Zn(Ⅱ) centers to form trinuclear structure which was further connected by hydrogen bonding to form two-dimensional structure. CCDC: 609515.     

由芳香羧酸和1,3,5-三咪唑基苯为配体构筑的锌、镉配合物的合成、结构和荧光性质

通过水热法得到了2个配位聚合物{[Zn(timb)(BTEC)_0.5]·H₂O}_n(1)和{[Cd(timb)(DPA)]·H₂O}_n(2)(timb=1,3,5-三咪唑基苯,H₄BTEC=均苯四甲酸,H₂DPA=2,2-联苯二甲酸),对它们进行了元素分析、红外光谱分析,并利用X射线衍射测定了它们的单晶结构。 配合物1属于三斜晶系,P1空间群。配合物2属于单斜晶系,C2/c空间群。配合物1拥有一个不寻常的三维框架结构,其拓扑为(4.6³·8⁶)₂(4²·8⁴)(6³)₂;而配合物2具有一维单层纳米管结构。结果说明了金属离子和有机羧酸配体在配合物组装过程中起着非常重要的作用。此外,在室温下对2个配合物进行了荧光性质分析。     

一维配合物{[Cd(BDC)(bpimb)_(0.5)(H_2O)]·H_2O}_n的水热合成、晶体结构和荧光性质研究(英文)

水热合成了一个新配合物{[Cd(BDC)(bpimb)0.5(H2O)]·H2O}n。通过元素分析、红外光谱、热重以及X-射线单晶洐射对其进行了表征.该晶体属单斜晶系,P21/c空间群。Cd髤原子通过BDC和bpimb两种配体连接成一维带状结构,带与带之间通过O-H…O和C-H…O连接成三维超分子结构。室温下配合物具有较强的荧光发射光谱。     

以樟脑酸及咪唑基化合物为配体的锌配合物的合成、晶体结构及荧光性质

以硝酸锌、樟脑酸(H2CAM)和1,2-二咪唑基二甲苯(obix)或4,4′-二咪唑基二甲联苯(bimb)为原料,在水热条件下得到2个结构不同的配位聚合物[Zn(obix)(CAM)]n(1)和[Zn(bimb)(CAM)]n(2)。对它们进行了元素分析、红外光谱和热重等分析,并利用X-射线洐射测定了它们的单晶结构。配合物1中2个锌离子通过2个obix配体桥连成一个24元大环,它再通过CAM配体连接成一维管状结构,而配合物2中锌离子通过两种配体桥连成二维层状结构。结果说明了辅助配体在配合物组装过程中起着非常重要的作用。此外还研究了它们的荧光性质。     

Cadmium(II) and copper(II) complexes with imidazole-containing tripodal polyamine ligands: pH and anion effects on carbon dioxide fixation and assembling

A new Cd(II) complex [Cd3(L)3(mu3-CO3)](ClO4)4.2CH3CN (1) with two-dimensional (2D) network structure was obtained by reaction of an imidazole-containing tripodal polyamine ligand N1-(2-aminoethyl)-N1-(2-imidazolethyl)-ethane-1,2-diamine (L) with Cd(ClO4)2.6H2O at pH 9.0 in air. The carbonate anions (CO3(2-)) are from the hydration of the atmospheric carbon dioxide, which is the same as in the previously reported Cu(II) complex [Cu3(L)3(mu3-CO3)](ClO4)4.3CH3CN (2). However, the coordination mode of CO3(2-) in 1 is mu3-eta2:eta2:eta2 while the one in 2 is mu3-eta1:eta1:eta1. One-dimensional (1D) chain Cd(II) and Cu(II) complexes [Cd(L)Cl]ClO4.H2O (3) and [Cu(L)(H2O)](ClO4)2 (4) without CO3(2-) were prepared by a similar method as that for 1 and 2 except for the different reaction pH, namely, 3 and 4 were obtained at pH 7 while 1 and 2 were obtained at pH 9. In addition, when Cu(NO3)2 was used to react with L at pH 9, a unique 1D double-stranded helical chain complex [Cu(L)Cl]NO3.1.25H2O (5) was obtained. The results revealed that the reaction pH and the counteranion have great impact on the carbon dioxide absorption and hydration as well as on the assembling and structure of the complexes. The magnetic property of complex 2 was investigated in the temperature range of 1.8-300 K, and weak ferromagnetic coupling among the mu3-eta1:eta1:eta1-CO3(2-) bridged Cu(II) atoms was observed.