一维链状锰配位聚合物的合成、晶体结构及热稳定性研究

A manganese coordination polymer, [Mn(C₇H₂I₃O₂)₂(CH₃OH)₂]_n was synthesized and characterized by the element analysis, IR, TG and single crystal X-ray diffraction structure analysis. The title complex crystallizes in monoclinic system with space group P2₁/c, a=0.461 66(9) nm, b=1.716 6(3) nm, c=1.647 5(3) nm, β=91.84(3)°, and V=1.305 2(4) nm³, Z=2, R=0.026 2, wR=0.063 4. Each manganese(Ⅱ) ion exists in an octahedral geometry with four O atoms from three different triiodobenzoate groups and two O atoms from two methanol molecules. Two adjacent manganese(Ⅱ) atoms are bridged by two triiodobenzoate groups in bis-monodentate mode, constructing a one-dimensional chain structure along a axis, with the adjacent Mn…Mn distance being 0.461 7(5) nm. Moreover, the weak interactions between the iodine atoms lead to a three-dimensional supramolecular network. CCDC: 666558.     

一维链状铜配位聚合物的合成、晶体结构与热稳定性研究

本文合成了1个新的一维配位聚合物[Cu(apy)(sal)2]n(apy=2-氨基嘧啶,sal=水杨醛),并对其进行了元素分析、红外、热重、紫外、核磁、粉末XRD及单晶X-射线衍射表征。该聚合物为三斜晶系,空间群P1,a=0.726 87(15)nm,b=0.914 41(18)nm,c=1.382 0(3)nm,α=108.74(3)°,β=94.13(3)°,γ=96.64(3)°,V=0.858 2(3)nm 3,Z=2,R=0.087 8。Cu(Ⅱ)离子分别与来自2个不同水杨醛配体中的4个氧原子以及2个不同2-氨基嘧啶配体中的2个氮原子配位,形成了1个八面体配位构型。2-氨基嘧啶配体桥联相邻的Cu(Ⅱ)离子形成了沿bc平面的一维折叠链状结构,其相邻Cu(Ⅱ)离子之间的距离为0.6954 nm。此外,相邻的链中水杨醛的芳环之间存在着π-π堆积作用,该芳环堆积作用使得配合物构筑成二维超分子层状结构。     

一维链状配位聚合物[Ni(p-CPOA)(2,2''''-bipy)(H_2O)]_n的合成与晶体结构

合成了一个新的配位聚合物[Ni(p-CPOA)([(2,2)0(')]-bipy)(H2O)]n(p-CPOA= 4-羧基苯氧乙酸根[(, )(2,2)0(')( )]-bipy= [(2,2)0(')( )]-联吡啶), 并对其进行了元素分析、红外和单晶 X-射线的表征。结果表明:配合物的化学式为C19H16N2O6[(Ni)(, /c, 晶胞参数[(a)( )]= 14.254(3), b = 13.085(3), c = 19.372(4) ? ?= 104.89(3),V = 3491.8(12) 3, Z = 8, Mr = 427.05, Dc = 1.625 g/cm3, μ = 1.153mm-1, F(000) = 1760, 最终R = 0.0345, wR = 0.0565。Ni原子为扭曲的六配位八面体构型, 每个p-CPOA2-配体桥联2个Ni原子形成一维折叠链状结构[(, )22.7(Ni)]…Ni原子之间的距离为[(9.67)(5)], 且通过分子间氢键将一维链连接成双链结构。     

两种铜配位聚合物的晶体结构和量子化学计算

在水热条件下以4-硝基邻苯二甲酸（4-H₂nph）/2,2''-联吡啶-4,4''-二甲酸（H₂bda）为主要配体,3-（2-吡啶基）吡唑（HL）/1,4-双（咪唑基-1-基）丁烷（bib）为辅助配体制备了2种新的金属有机配位聚合物[Cu₄（4-nph）（L）₆]_n （1）和{[Cu₂（bda）₂（bib）₂（H₂O）₄]·4H₂O}_n （2）。通过元素分析、红外光谱、热重X射线单晶衍射和X射线粉末衍射对它们进行了表征。结果表明,配合物1属于单斜晶系,C2/c空间群。晶胞参数：a=1.956 16（8） nm,b=1.290 68（8） nm,c=2.160 34（12） nm,β=97.073（2）°,V=5.412 9（5） nm³,Z=4。配合物2属于三斜晶系,P1空间群。晶胞参数：a=0.962 22（15） nm,b=1.102 90（17） nm,c=1.404 3（2） nm,α=72.752（4）°,β=79.271（4）°,γ=67.065 （3）°,V=1.306 6（4） nm³,Z=1。在配合物1中,羧基配体4-nph^2-通过单齿模式桥联金属中心,形成一维结构。在配合物2中,柔性bib配体连接金属中心形成具有26元环的双核结构。此外,还用Gaussian16程序PBE0/LANL2DZ方法从配合物1的晶体结构中提取“分子片段”进行了量子化学计算。计算结果表明配位原子与铜（Ⅱ）离子之间存在着共价作用。     

一维链状配位聚合物[Ni(p-CPOA)(2,2′-bipy)(H2O)]n的合成与晶体结构

合成了一个新的配位聚合物[Ni(p-CPOA)(2,2′-bipy)(H2O)]n(p-CPOA2-= 4-羧基苯氧乙酸根,2,2′-bipy= 2,2′-联吡啶),并对其进行了元素分析、红外和单晶X-射线的表征.结果表明:配合物的化学式为C19H16N2O6Ni,晶体属单斜晶系,空间群为C2/c,晶胞参数a = 14.254(3),b = 13.085(3),c = 19.372(4)A,β = 104.89(3)°,V = 3491.8(12)A3,Z = 8,Mr = 427.05,Dc = 1.625 g/cm3,μ = 1.153mm－1,F(000) = 1760,最终R = 0.0345,wR = 0.0565。Ni原子为扭曲的六配位八面体构型,每个p-CPOA2－配体桥联2个Ni原子形成一维折叠链状结构,Ni…Ni原子之间的距离为9.675A,且通过分子间氢键将一维链连接成双链结构.     

一种新型Ni(Ⅱ)配位聚合物的合成、晶体结构和性质研究

溶剂热法合成了1个新配位聚合物{[Ni(C18H18N4O5)(DMF)]·(DMF}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.该晶体为正交晶系,Pna21空间群.该化合物中,C18H18N4O5配体通过5个配位原子以及相邻的溶剂分子DMF上的1个配位原子与Ni(Ⅱ)原子配位,形成了1个扭曲的八面体配位构型.热重分析表明该化合物在140℃开始发生分解.     

金属离子导向合成两个金属配位聚合物:晶体结构和荧光性质

以2,5-呋喃二羧酸和六水硝酸锌/四水硝酸镉为原料,在溶剂热条件下,合成出2个金属有机配位聚合物,[Zn（FDC）（DMF）₂]_n（1）和{（Me₂NH₂）₂[Cd₂（FDC）₃（H₂O）₂]·4H₂O}_n（2）（H₂FDC=2,5-呋喃二甲酸,DMF=N,N-二甲基甲酰胺）。通过元素分析、红外光谱、差热分析、X射线粉末衍射和X射线单晶衍射等手段对配合物进行了结构表征。结果显示,化合物1为一维链结构,通过分子间氢键作用构筑成二维结构;而2为二维（4,4）网络结构。热稳定性表明化合物1脱去DMF配体后稳定到300 ℃;而2脱去配体水、阴离子和溶剂分子后结构立即发生坍塌。常温固态下,激发波长分别为303 和350 nm时考察了配合物1和2的荧光性质,结果显示2个化合物均发射蓝色荧光（λ_max=406,470 nm）,荧光寿命分别为76.2和138.1 ns。     

金属离子导向合成两个金属配位聚合物:晶体结构和荧光性质

以2,5-呋喃二羧酸和六水硝酸锌/四水硝酸镉为原料,在溶剂热条件下,合成出2个金属有机配位聚合物,[Zn (FDC)(DMF)₂]_n(1)和{(Me₂NH₂)₂[Cd₂(FDC)₃(H₂O)₂]·4H₂O}_n(2)(H₂FDC=2,5-呋喃二甲酸,DMF=N,N-二甲基甲酰胺)。通过元素分析、红外光谱、差热分析、X射线粉末衍射和X射线单晶衍射等手段对配合物进行了结构表征。结果显示,化合物1为一维链结构,通过分子间氢键作用构筑成二维结构;而2为二维(4,4)网络结构。热稳定性表明化合物1脱去DMF配体后稳定到300℃;而2脱去配体水、阴离子和溶剂分子后结构立即发生坍塌。常温固态下,激发波长分别为303和350 nm时考察了配合物1和2的荧光性质,结果显示2个化合物均发射蓝色荧光(λ_max=406,470 nm),荧光寿命分别为76.2和138.1 ns。     

d10金属构筑的配位聚合物的合成与晶体结构

利用水热合成方法合成了2个新的配位聚合物[Ag(4,4′-bpy)(H2PO4)].2H2O(1)和[Cu4(L)8H4](2)(4,4′-bpy=4,4′-联吡啶,L=4-咪唑基苯甲酸),并通过元素分析、红外光谱和X-射线单晶衍射方法确定了该化合物的晶体结构.结构分析表明化合物1属于单斜晶系,P2/c空间群,晶胞参数a=8.490 9(17)nm,b=8.728 4(17)nm,c=18.498(4)nm,β=100.99(3)°,V=1.345 8(5)nm3,Z=4,R1=0.036 2,ωR2=0.096 6.化合物1展示了一个一维的链式结构.化合物2属于单斜晶系,C2/c空间群,晶胞参数a=24.509(5)nm,b=18.957(5)nm,c=17.246(5)nm,β=119.807(5)°,V=6.953(3)nm3,Z=4,R1=0.045 5(3564),ωR2=0.151 9(6161).化合物2中存在着丰富的π…π堆积作用.     

柔性配体癸二酸构筑的镍多孔配位聚合物的合成和晶体结构

由硫酸镍和癸二酸(C10H18O4)合成了配合物:[Ni(C10H16O4)(H2O)4].1.5H2O,并通过元素分析、红外光谱、热重分析对其进行表征,用单晶X-射线衍射方法测定了配合物的晶体结构。配合物属于正交晶系,空间群Cmca,晶胞参数:a=0.753820(10)nm,b=1.076 97(2)nm,c=4.130 42(8)nm,晶胞体积:V=3.353 25(10)nm3,晶胞内结构基元数Z=4,分子量Mr=358.02,电子数F(000)=1 528,密度Dc=1.418 g·cm-3,吸收系数μ(Mo Kα)=1.195 mm-1。     

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.     

Syntheses,Structures and Magnetic Properties of Two Coordination Polymers Based on 2, 2-Biphenyldicarboxylate Ligand

Two coordination polymers {[Co₃L₃(Me₂NH)₂]·(Me₂NH)}_n(1) and [CuL(bpy)]_n(2)(L=2,2'-biphenyl dicarboxylate ion, bpy=4,4'-bipyridine) were obtained and characterized. Compound 1 was synthesised via solvothermal method, with the L ligands adopting syn-syn-μ₂-η¹:η¹- and μ₂-η²-coordination modes and Co(II) centers being linked to form a 1D coordination chain with trinuclear Co₃ cluster as sub-units. Compound 2 was synthesized at room temperature, with the L ligand chelating the Cu(II) centers to form a 1D chain, which was further linked by the auxiliary 4,4'-bpy ligand to form a 3D coordination network. The results of variable temperature susceptibility studies reveal that there were ferromagnetic and antiferromagnetic interactions between the paramagnetic metal centers in compounds 1 and 2, respectively.     

Two CdII/CoII‐Imidazolate Coordination Polymers: Syntheses,Crystal Structures,Stabilities, and Luminescent/Magnetic Properties

Cadmium(II) based 2D coordination polymer [Cd(L1)₂(DMF)₂] ( 1 ) (L1 = 4,5‐dicyano‐2‐methylimidazolate, DMF = N,N′‐dimethylformamide) and 2D cobalt(II)‐imidazolate framework [Co(L3)₄] ( 2 ) (L3 = 4,5‐diamide‐2‐ethoxyimidazolate) were synthesized under solvothermal reaction conditions. The materials were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction measurement (PXRD) and single‐crystal X‐ray diffraction. Compound 1 has hexacoordinate Cd^II ions and forms a zigzag chain‐like coordination polymer structure, whereas compound 2 exhibits a 2D square grid type structure. The thermal stability analysis reveals that 2 showed an exceptional thermal stability up to 360 °C. Also, 2 maintained its fully crystalline integrity in boiling water as confirmed by PXRD. The solid state luminescent property of 1 was not observed at room temperature. Compound 2 showed an independent high spin central Co^II atom.     

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.     

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.     

Tuning the Topological Net via the Metal Ion‐Driven Assembly of Two ZnII / CdII Coordination Polymers: Syntheses,Crystal Structures,and Luminescent Properties

The coordination polymers {[Zn₂(HIDC)₂(tib)] · H₂O}_n ( 1 ) and {[Cd(HIDC)(tib)] · H₂O}_n ( 2 ) [H₃IDC = 1H‐imidazole‐4, 5‐dicarboxylic acid, tib = 1, 3,5,‐tris(1‐imidazolyl) benzene] were obtained under hydrothermal conditions. Their structures were determined by single‐crystal X‐ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy. Complex 1 exhibits a two‐dimensional layer structure with a 6³‐hcb topology. Complex 2 has a three‐dimensional structure with a pcu topology. It is shown that the carboxylate ligand can bear diverse structures regulated by metal ions. Additionally, the photoluminescence behaviors of complexes 1 and 2 are discussed.     

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.     

两个镉的配位聚合物的原位水热合成、晶体结构与荧光性质

在水热条件下, 以3-氨基-1,2,4-三唑-5-甲酸(AmTHZAC)为配体, 原位反应得到了两个镉的配位聚合物 Cd(AmTAZ)Cl(1)和[Cd(AmTAZ)(BDC)(H2O)2]·1.25H2O(2)(AmTAZH=3-amino-1,2,4-triazole, H2BDC=benzene-1,4-dicarboxylic acid), 采用红外光谱、差热-热重、CHN元素分析及单晶X射线衍射等手段对晶体结构进行了表征, 并研究了化合物1和2的荧光性质. 化合物1属正交晶系, P2(1)2(1)2(1)空间群, a=0.6452(3) nm, b=0.7848(5) nm, c=1.0449(6) nm, V=0.5291(5) nm3, Z=4, 最后一致性因子[I＞2σ(I)], R1=0.0226, wR2=0.0377, GOF=1.087. 化合物2属正交晶系, Pmc2(1)空间群, a=0.7100 nm, b=0.9920 nm, c=1.2561 nm, V=0.8847 nm3, Z=8, 最后一致性因子[I＞2σ(I)], R1=0.0934, wR2=0.2456, GOF=1.031.     

Two Coordination Polymers based on a Carboxylate‐­functionalized Imidazophenanthroline Derivative Ligand and Phthalic Acid: Syntheses,Structures and Magnetic Properties

Two coordination polymers, [Co₂(Hcpip)₂(phth)]_n · 3n(H₂O) ( 1 ) and [Mn₂(Hcpip)₂(phth)]_n ( 2 ), {H₂cpip = 2‐(2‐carboxyphenyl)imidazo[4,5‐f](1,10)‐ phenanthroline, H₂phth = phthalic acid}, were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. Complex 1 is a 1D chain, in which the dinuclear [Co₂(Hcpip)₂]²⁺ units are linked through (phth)^2– anions. Complex 2 is a 2D layer structure, which is constructed from the 1D chains bridged by (phth)^2– anions. The magnetic properties of 1 and 2 show that the weak ferromagnetic interactions occurred between Co^II ions in 1 and a weak antiferromagnetic interactions exist between Mn^II ions in 2 . These two complexes have good thermal stabilities.     

两个一维之字链异三金属配位聚合物的合成、结构和磁性

用分步合成法得到了2个结构新颖的一维之字链异三金属配位聚合物{[Cu(Me_2valpn)Dy(DMF)_2(H_2O)Fe(CN)_6]·1.5H_2O·0.5CH_3OH}n(1)和{[Cu(Me_2valpn)Tb(DMF)_2(H_2O)Fe(CN)_6]·H_2O·CH_3OH}n(2)(H_2Me_2valpn=N,N′-双(3-甲氧基-水杨醛)缩-2,2-二甲基-1,3-丙二胺)。X射线单晶衍射分析表明每个[Fe(CN)_6]3-用顺式的2个氰根分别连接2个相邻构筑单元[Cu(Me_2valpn)Ln(DMF)_2(H_2O)]_3+的Cu(Ⅱ)和Ln(Ⅲ)。除了Cu(Ⅱ)和Ln(Ⅲ)之间的双酚氧桥之外,链中还包含Fe-C≡N-Cu和Fe-C≡N-Ln两类弯曲的桥联结构。配合物1在9.5~300 K的直流变温磁化率数据符合居里-韦斯定律,韦斯常数(θ)为13.17 K,表明配合物1总体上表现铁磁相互作用。交流磁化率测试表明配合物1没有表现出缓慢磁弛豫现象。