Syntheses,Crystal Structures and Photophysical Properties of a Series of Cadmium(II) Coordination Polymers

Three cadmium(II) coordination polymers [Cd(NA)₂(H₂O)₂]_n ( 1 ), {[Cd(NA)(phen)(NO₃)]·(H₂O)_1/2}_n ( 2 ), {[Cd(NA)(CH₃C₆H₄COO)(H₂O)₂]·(CH₃C₆H₄COOH)}_n ( 3 ) (HNA = nicotinic acid, phen = 1, 10‐phenanthroline) have been synthesized by hydrothermal method. Their single‐crystal structures were determined by X‐ray diffractometry. The absorption, excitation and emission spectra were investigated and all the complexes emit strong fluorescence: λ^em_max = 544 nm (λ^ex = 492 nm), 1 ; λ^em_max = 466 nm (λ^ex = 393 nm), 2 ; λ^em_max = 430 nm (λ^ex = 313 nm), 3 . At room temperature in the solid state the fluorescence lifetimes of the complexes were investigated and the relationships between the spectra were discussed as well as the connections of luminescence and crystal structures.     

Silver(I) Complexes with Dithioether Ligands: Syntheses,Crystal Structures,and Fluorescence Properties

Two new dithioether ligands, 1,4‐bis[(phenylsulfanyl)methyl]naphthalene ( L¹ ), and 4,4′‐bis[(tert‐butylsulfanyl)methyl]biphenyl ( L² ) were synthesized and their silver(I) complexes were studied. Both Ag^I complexes, [Ag L¹ (NO₃)]_n ( 1 ) and [Ag L² (NO₃)]₂ ( 2 ), were synthesized at ambient temperature and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction analysis. Single‐crystal X‐ray analysis shows that complex 1 has a one‐dimensional helical chain structure with the neutral repeating unit [Ag(μ₂‐ L¹ )(NO₃)], whereas complex 2 has a centrosymmetrical neutral dinuclear structure. Moreover, complexes 1 and 2 are further extended into three‐dimensional supramolecular frameworks by hydrogen bonding and π–π stacking interactions, respectively. In addition, complexes 1 and 2 display strong blue emission in the solid state at room temperature.     

Two 1D Ladderlike Heterometallic Zinc(II) Coordination Polymers: Syntheses,Crystal Structures,and Fluorescence Properties

Two coordination polymers [Zn₂(ipt)₂(CuL)₂(H₂O)] ( 1 ) and [Zn₂(ipt)₂(NiL)₂(H₂O)] ( 2 ) (ML, H₂L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclo‐pentadeca‐7,13‐dien; H₂ipt = isophthalic acid) were synthesized by solvothermal methods and characterized by single‐crystal X‐ray diffraction. Complexes 1 and 2 exhibit ladderlike chains, consisting of Zn₄Cu₄ and Zn₄Ni₄ units, respectively, which are connected via oxamide and isophthalate. These chains are further interlinked by hydrogen bonds resulting in a 2D supramolecular architecture. The fluorescence properties of compounds 1 and 2 are also discussed.     

Syntheses,Structures and Luminescent Properties of 2D and 3D Cadmium(II) Coordination Polymers Derived from Two Isomeric Perchlorinated Benzenedicarboxylates

The coordination polymers {[Cd(o‐BDC‐Cl₄)(H₂O)₂]·EtOH}_n ( 1 ) and {[Cd(p‐BDC‐Cl₄)(DMF)]·H₂O}_n ( 2 ) (o‐BDC‐Cl₄ = tetrachlorophthalate and p‐BDC‐Cl₄ = tetrachloroterephthalate) were synthesized in different solvents using two isomeric tetrachlorinated benzenedicarboxylic acids. Complex 1 based on o‐BDC‐Cl₄ features an extremely rare 2D trinodal (3,4,6)‐connected network constructed by the combination of 1D [Cd‐H₂O]_n chains and 1D [Cd₂(o‐BDC‐Cl₄)₂]_n loop‐like motifs. Complex 2 based on p‐BDC‐Cl₄ has a 3D framework and shows a uninodal 4‐connected sra topology. Complexes 1 and 2 were characterized by elemental analyses, IR spectroscopy, single‐crystal X‐ray diffraction and thermogravimetric (TG) analyses. The photoluminescence of 1 and 2 were investigated in the solid state at room temperature.     

Tuning Structural Topologies of Two Cadmium(II) Coordination Polymers via Isomeric Dipyridyl Ligands: Syntheses,Crystal Structures,and Luminescent Properties

Abstract. Two new coordination polymers {[Cd₂(BDC)₂(3‐bpmp)(H₂O)₂] · 2H₂O}_n ( 1 ) and [Cd₂(BDC)₂(4‐bpmp)]_n ( 2 ) [H₂BDC = 5‐hydroxy‐isophthalic acid, 3‐bpmp = 1,4‐bis(3‐pyridylmethy)piperazine, and 4‐bpmp = 1,4‐bis(4‐pyridylmethy) piperazine] were synthesized via hydrothermal synthesis, and further characterized by IR spectroscopy, elemental analysis, XRD, and X‐ray crystallography. Complex 1 shows a two‐dimensional (4,4) sql topology and complex 2 features an 8‐connected hex topology. Moreover, the luminescent properties of complexes 1 and 2 were investigated in the solid state at room temperature.     

基于N-乙酸基-5-氧烟酸的两个Pb(II)配位聚合物的合成、晶体结构与荧光性质

采用水热法合成了2个以N-乙酸基-5-氧烟酸（H₂L）为配体的铅金属-有机配位聚合物：[Pb₄（μ₃-O）₂L₂]_n（1）和[Pb₃（μ₄-O）₂L]_n（2）。通过元素分析、红外光谱和X射线单晶衍射进行了结构表征。结构分析表明,聚合物₁属单斜晶系,C2/c空间群,其由[Pb₄（μ₃-O）₂]_n构成的刚性无机链通过配体L^2-连接成三维网络结构。聚合物₂属正交晶系,P2₁2₁2₁空间群,其三维结构由[Pb₃（μ₄-O）₂]_n构成的无机金属链与配体L^2-相互连接形成。研究了2的热稳定性及其在室温下的固体荧光性质。     

Syntheses,Crystal Structures,and Luminescent Properties of ZnII/CdII Coordination Polymers with Different Interpenetrating Networks

Zn^II and Cd^II coordination polymers with dicarboxylate and imidazole‐containing ligands, namely, [Cd (2,3‐PDC)(L)]_n ( 1 ) and {[Zn(3,4‐PDC) (L)_0.5] · H₂O}_n ( 2 ), [2,3‐H₂PDC = 2,3‐pyridine dicarboxylate, 3,4‐H₂PDC = 3,4‐pyridine dicarboxylate, and L = 1,4‐bis(2‐methylimidazol‐3‐ium‐1‐yl)biphenyl], were prepared and characterized by elemental analysis, IR spectroscopy, and X‐ray diffraction. Complex 1 shows a three‐dimensional (3D) structure with threefold interpenetrating diamond topology. Complex 2 features a 3D framework with twofold interpenetrating dmc topology. Moreover, the luminescent properties of complexes 1 and 2 were also investigated.     

Syntheses,Characterization and Crystal Structures of Three Structurally Similar Dinuclear Schiff Base Cadmium(II) Complexes with Bridging Azide or Thiocyanate Ligands

Three novel Schiff base cadmium(II) complexes, derived from the end‐on (μ‐1,1‐N₃) azide or end‐to‐end (μ‐1,3‐NCS) thio cyanate bridges and similar tridentate Schiff base ligands, have been synthesized under similar synthetic procedures and their crystal structures determined by X‐ray diffraction methods. They are the dinuclear double end‐on azide‐bridged [Cd₂(L1)₂(N₃)₂(μ‐1,1‐N₃)₂] ( 1 ), the dinuclear double end‐on azide‐bridged [Cd₂(L2)₂(N₃)₂(μ‐1,1‐N₃)₂] ( 2 ), and the dinuclear double end‐to‐end thiocyanate‐bridged [Cd₂(L3)₂(NCS)₂(μ_1,3‐NCS)₂] ( 3 ), where L1, L2 and L3 are three similar tridentate Schiff bases obtained by condensation of 2‐pyridylaldehyde with N,N‐diethylethane‐1,2‐diamine, of 2‐pyridylaldehyde with N‐isopropylethane‐1,2‐diamine, and of 2‐pyridylaldehyde with N,N‐dimethylpropane‐1,3‐diamine, respectively. Each cadmium(II) centre in the complexes is in a distorted octahedral coordination. There is a crystallographic inversion centre in each of the complexes. The similar small ligands used as the secondary ligands in the preparation of the cadmium(II) complexes with similar Schiff bases can result in similar structures.     

Crystal Structures and Photoluminescence Properties of Zinc(II) and Cadmium(II) Coordination Polymers with “Y”‐Shaped Ligands

Three Zn^II and Cd^II complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L₁)(2,2′‐bpy)₂(H₂O)] · 2H₂O ( 1 ), [Zn(L₁)(bpp)(H₂O)] ( 2 ), and [Cd(L₁)(H₂O)] · H₂O ( 3 ) [H₂L₁ = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H ··· O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.8²). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1 – 3 were also investigated.     

基于3-氧醚乙酸-邻苯二酸和N-辅助配体的锌和镉配合物的合成、晶体结构及荧光性质

水热法合成得到2个配合物, {[Zn₇(L)₄(bpe)₂(μ₃-OH)₂(H₂O)₈]·4H₂O}_n(1), 和{[Cd₃(L)₂(bpy)_2.5(H₂O)]·5.5H₂O}_n(2)(H₃L=3-(carboxymethoxy)benzene-1,2-dioic acid, bpe=1,2-bis(4-pyridyl)-ethene, bpy=4,4'-bipyridine), 并采用元素分析、红外光谱、热重和X-射线单晶衍射对其结构进行表征。配合物1中, 配体L^3-和bpe连接[Zn₅( μ₃-OH)₂]中心形成一维链, 这样的链通过氢键连接成三维的超分子结构。配合物2呈现(3,3,6)连接的网状结构。此外, 对配合物1和2的荧光性质进行了研究。     

Influence of the Different Dicarboxylate Ligands on The Topological Net of Manganese(II) Coordination Polymers: Syntheses,Crystal Structures. and Luminescent Properties

The self‐assembly of Mn^II ions and 1,4‐bis(2‐methyl‐imidazole‐1‐yl)benzene (bip) with two different dicarboxylate ligands, benzophenone‐4,4′‐dicarboxylic acid (H₂bda) and 1,4‐naphthalenedicarboxylic acid (H₂nda) via hydrothermal synthesis resulted in two interesting coordination polymers, [Mn(bda)(bip)]_n ( 1 ) and [(Mn(nda)(bip)_0.5(H₂O)]_n ( 2 ). Their structures were determined by single‐crystal X‐ray diffraction and elemental analyses, as well as IR spectroscopy. Complex 1 exhibits an unusual polycatenated 2D+2D→3D framework. Complex 2 shows a twofold interpenetrated pcu net. In addition, the solid‐state photoluminescent properties of 1 and 2 were investigated at room temperature.     

基于3-氧醚乙酸-邻苯二酸和N-辅助配体的锌和镉配合物的合成、晶体结构及荧光性质

水热法合成得到2个配合物,{[Zn7(L)4(bpe)2(μ3-OH)2(H2O)8]·4H2O}n(1),和{[Cd3(L)2(bpy)2.5(H2O)]·5.5H2O}n(2)(H3L=3-(carboxymethoxy)benzene-1,2-dioic acid,bpe=1,2-bis(4-pyridyl)-ethene,bpy=4,4′-bipyridine),并采用元素分析、红外光谱、热重和X-射线单晶衍射对其结构进行表征。配合物1中,配体L3-和bpe连接[Zn5(μ3-OH)2]中心形成一维链,这样的链通过氢键连接成三维的超分子结构。配合物2呈现(3,3,6)连接的网状结构。此外,对配合物1和2的荧光性质进行了研究。     

Syntheses,Structures, and Photoluminescence of Two Three‐dimensional Cadmium Coordination Polymers with Benzene­dicarboxylate Ligands

Two cadmium(II) coordination polymers, namely, [Cd₃(m‐phth)₂(atz)₂]_n ( 1 ) (m‐phth = m‐phthalate and atz = 3‐amino‐1,2,4‐triazolate) and [Cd(atphth)(H₂O)]_n ( 2 ) (atphth = 2‐aminoterephthalate), were synthesized and structurally characterized. Compound 1 features a three‐dimensional (3D) pillared framework based on two‐dimensional (2D) cadmium‐benzenedicarboxylate ladders pillared by the triazolate ligands. Compound 2 has a 3D framework constructed from 2D cadmium‐benzenedicarboxylate layers, which are further linked by Cd–N bonds between the cadmium ions and amino groups of the atphth^2– ligands of the adjacent layers to form the final 3D structure. Compounds 1 and 2 exhibit solid‐state photoluminescence with emission maxima at 448 and 470 nm, respectively.     

Solvothermal Syntheses,Crystal Structures,and Luminescent Properties of Two Coordination Polymers with Different Interpenetrated Diamond Topology

Two coordination polymers, namely, {[Zn(bpea) (bmp)] · H₂O}_n ( 1 ) and {[Ni(bpea)(bimb)] · DMF}_n ( 2 ) [H₂bpea = biphenylethene‐4,4′‐dicarboxylate, bmp = 1,4‐bis(2‐methylimidazol‐3‐ium‐1‐yl)biphenyl and bimb = 1,4‐bis(1‐imidazol‐yl)‐2,5‐dimethyl benzene], were synthesized under solvothermal conditions with mixed organic ligands. Single crystal X‐ray diffraction reveals that complex 1 features a three‐dimensional (3D) structure with a sixfold interpenetrating dia net. Complex 2 shows a 3D fivefold interpenetrating dia topology. Furthermore, the solid state luminescent properties of complexes 1 and 2 were investigated at room temperature.     

两个由醋酸根和含吡啶基配体构筑的Zn(II)配聚物的合成、晶体结构及其荧光性质

以醋酸锌、异烟肼（INH）、2-氨基吡啶（2-APy）为原料在N,N-二甲基甲酰胺（DMF）溶液中合成了2个Zn（Ⅱ）配位聚合物[Zn（CH₃COO）₂（INH）]_n（1）,[Zn（CH₃COO）₂（2-APy）]_n（2）,用红外光谱、元素分析、粉末X射线衍射、X射线单晶衍射对配合物进行了表征。晶体结构测试表明,配聚物1属单斜晶系,空间群P2₁/c,晶胞参数：a=0.914 44（17）nm,b=0.161 86（3）nm,c=0.871 75（16）nm,β=96.181（3）°,V=1.282 8（4）nm³,Z=4;配聚物为2D层状结构,该层状结构通过氢键弱相互作用,进一步形成3D超分子结构。配聚物2属三斜晶系,空间群P1,晶胞参数：a=0.747 0（4）nm,b=0.814 5（5）nm,c=1.895 7（11）nm,α=88.276（8）°,β=86.202（8）°,γ=84.334（8）°,V=1.144 9（11）nm³,Z=2;配聚物2为一维zig-zag链状结构。室温固态荧光测试显示,配聚物1、2分别在最大波长382.6和367.5 nm处具有较强的荧光发射。     

Syntheses,Characterization, and Fluorescence Properties of Four Coordination Polymers based on Double Betaine Ligands

Four novel In³⁺ and Cd²⁺ based 1D coordination compounds constructed by double betaine ligands were synthesized and characterized structurally and optically. They assemble into 3D supra‐molecular architectures via different stacking or entanglement of 1D zigzag shaped chains, in which C–H ··· Cl and C–H ··· O hydrogen bonding interactions play a dramatic impact. Compound 1 displays a 1D + 1D → 3D four‐connect lvt net with 4² · 8⁴ topology. Compound 2 assembles into a 3D architecture by inclined stacking of the adjacent zigzag chains. Compound 3 displays a 2D + 2D → 3D inclined polycatenation based on the resulting 2D (6, 3) layers that constructed by 1D chains. Compound 4 displays a 3D supra‐molecular architecture based on 1D chains, which were connected via the hydrogen bonding. Meanwhile, four compounds emit in the range of visible region owing to the intra‐ligand π*→π and/or π*→n electron transition induced florescence.     

Syntheses,Structures, and Properties of Five Coordination Polymers Involving Phthalic Acid

Five new coordination polymers Cu(phen)(H2O)(phth)·CH3OH(1), [Cu(2,2'-bipy)(H2O)](phth)·3.5H2O(2), Zn(phen)(phth)(H2O)·1.125H2O(3) and [M(4,4'-bipy)(H2O)2](phth)·2H2O[M=Zn(4), Mn(5)](H2phth=phthalic acid, bipy=bipyridine, phen=1,10-phenanthroline) have been synthesized from the amino acid derivatives(phthalyl-l- valine, H2L) and structurally characterized. H2L was hydrolyzed into phth2– group during the reaction, but the strucure feature was different from that of the complex directly synthesized from H2phth in the reported literature, revealing that H2L played an important role in composing the novel compounds. Compounds 1, 2 and 3 are all 1D chains, but the differences are that compound 1 is further hydrogen-bonded into 2D networks, and compound 2 is further extended into 3D supramolecular network through π-π stacking and hydrogen-bonding interactions. However, compound 3 is a 1D helix chain structure and further links into 2D networks through π-π stacking. Compounds 4 and 5 are isostructural and exhibit the same 2D layers, which are further connected by hydrogen-bonding interactions to form 3D supramolecular network. Antiferromagnetic superexchange was observed for compounds 1, 2 and 5.     

Four 1D and 2D Cadmium(II) Complexes Based on Different Anions and Two Modified Bipyridyl Ligands: Syntheses,Structures, Thermogravimetric,and Fluorescent Properties

A series of cadmium(II) coordination polymers constructed from 1, 3‐bis(pyridine‐3‐carbonyl)imidazolidin‐2‐thioxo (3‐bpit) and 1, 3‐bis(pyridine‐4‐carbonyl)imidazolidin‐2‐thioxo (4‐bpit), namely,{[Cd(SCN)₂(3‐bpit)₂] · 2(CH₃OH)}_n ( 1 ), {[Cd(NO₃)₂(3‐bpit)₂] · 2(CH₃OH)}_n( 2 ), [CdI₂(4‐bpit)]_n ( 3 ), and [CdCl₂(4‐bpit)₄]_n ( 4 ) were prepared and characterized by single‐crystal X‐ray diffraction. Complexes 1 and 2 display different types of infinite 1D helical chain structures, both of which contain 24‐membered metallocyclic rings. Complex 3 is composed of 1D zigzag chains, which further form a 3D supramolecular architecture by weak C–H ··· S and S ··· I interactions. Complex 4 also features a 3D supramolecular network assembled from 2D rhombus‐shaped layer through intermolecular hydrogen bonding. These structures indicate that the conformation of the ligand and the diverse anions take important roles in the formation of different frameworks. Thermogravimetric and fluorescent properties over complexes are also discussed.     

基于双(1,2,4-三氮唑基)刚性配体和芳香羧酸的两个配位聚合物的合成、晶体结构及荧光性质

水热条件下,合成了2个结构新颖的金属配位聚合物:[Co_1.5(btb)₂(nbta)(H₂O)₂]_n(1),[Cd(btb)_0.5(nph)(H₂O)]_n(2)(btb=4,4'-二(1,2,4-三氮唑-1-基)联苯,H₃nbta=5-硝基-1,2,3-苯三甲酸,H₂nph=3-硝基邻苯二甲酸)并对它们进行了元素分析,红外光谱及X-射线单晶衍射等表征。结构分析表明,化合物1是一个二维(3,4)-连接3,4L90拓扑结构,并进一步通过O-H…O氢键作用构筑成三维超分子结构。而配合物2是一个三维(3,4,4)-连接的sqc69网络,它的拓扑符号为(4.8²)₂(4².8².10²)(8.10⁴.12)。此外,还研究了这两个配合物的热重和荧光性质。     

基于双(1,2,4-三氮唑基)刚性配体和芳香羧酸的两个配位聚合物的合成、晶体结构及荧光性质

水热条件下,合成了2个结构新颖的金属配位聚合物:[Co_1.5(btb)₂(nbta)(H₂O)₂]_n(1),[Cd(btb)_0.5(nph)(H₂O)]_n(2)(btb=4,4'-二(1,2,4-三氮唑-1-基)联苯,H₃nbta=5-硝基-1,2,3-苯三甲酸,H₂nph=3-硝基邻苯二甲酸)并对它们进行了元素分析,红外光谱及X-射线单晶衍射等表征。结构分析表明,化合物1是一个二维(3,4)-连接3,4L90拓扑结构,并进一步通过O-H…O氢键作用构筑成三维超分子结构。而配合物2是一个三维(3,4,4)-连接的sqc69网络,它的拓扑符号为(4.8²)₂(4².8².10²)(8.10⁴.12)。此外,还研究了这两个配合物的热重和荧光性质。