含共轭三烯吡啶配体的配位聚合物的合成、结构及荧光性质

将1,6-双（4-吡啶基）-1,3,5-己三烯（bphte）和镉盐分别与2种羧酸配体（2,5-二呋喃二甲酸（2,5-H₂FDC）及1,3,5-均苯三甲酸（1,3,5-H₃BTC））进行溶剂热反应,得到2个配位聚合物：[Cd （2,5-FDC）（bphte）（H₂O）]_n （1）和[Cd （1,3,5-HBTC）（bphte）]_n （2）。对配合物1和2分别进行了元素分析、红外光谱、单晶X射线衍射、粉末X射线衍射和热重分析表征。配位聚合物1具有spl拓扑结构的三维互穿超分子框架,而配合物2是由bphte配体交叉连接一维链[Cd₂（1,3,5-HBTC）₂]_n形成的三维结构。配合物1和2在固态时表现出不同的荧光性质。配合物2遇到水溶液中Fe³⁺会发生荧光猝灭,因此以其作为荧光探针对水溶液中Fe³⁺进行了选择性荧光检测,它对Fe³⁺的检测限可达到0.013 μmol·L^-1。这种荧光猝灭过程可归因于Fe³⁺离子的吸收带与配合物2的激发带之间存在部分重叠。     

Effect of Anionic Ancillary Ligands on Terpyridine Based Coordination Polymers: Synthesis,Crystal Structure and Fluorescence Property

By using different anionic ancillary ligands, two new coordination polymers, [Cd(L)I_2]_n(1) and {[Cd(L)_2(1,4-bdc)]·H_2O}_n(2)(L = 2,4,6-tris(4-pyridyl)pyridine, 1,4-H_2bdc = benzene-1,4-dicarboxylic acid), have been synthesized under hydrothermal conditions. Compound 1 crystallizes in monoclinic, space group C2/c with a = 11.625(2), b = 13.871(3), c = 13.676(3) ?, β = 108.11(3)°, V = 2096.0(7) ?~3, D_c = 2.144 g/cm~3, C_(20)H_(14)I_2N_4Cd, M_r = 676.55, F(000) = 1264, μ(MoKα) = 3.999 mm~(–1), Z = 4, Rint = 0.0308,(Δρ)_(max) = 0.354,(Δρ)_(min) = 0.289, R = 0.0332 and wR = 0.0721 for 2401 observed reflections(I 2σ(I)). However, compound 2 crystallizes in triclinic, space group P1 with a = 10.315(2), b = 14.060(3), c = 15.090(3) ?, β = 98.40(3)o, V = 1990.0(9) ?~3, D_c = 1.527 g/cm~3, C_(48)H_(34)N_8O_5Cd, M_r = 915.23, F(000) = 932, μ(MoKα)= 0.610 mm~(–1), Z = 2, Rint = 0.0776,(Δρ)_(max) = 0.869,(Δρ)_(min) = 0.843, R = 0.0815 and wR = 0.1930 for 6999 observed reflections(I 2σ(I)). Compound 1 is a 1D chain structure, which adopts inorganic anion I- as the counterion, and 2 exists a 2D(4,4) network constructed by benzene-1,4-dicarboxylic acid.     

Carboxylate-Free Manganese(II) Phosphonate Assemblies: Synthesis, Structure, and Magnetism

The reaction of manganese(II) salts with organophosphonic acid [t-BuPO(3)H(2) or cyclopentyl phosphonic acid (C(5)H(9)PO(3)H(2))] in the presence of ancillary nitrogen ligands [1,10-phenanthroline (phen) or 2,6-bis(pyrazol-3-yl)pyridine (dpzpy)], afforded, depending on the stoichiometry of the reactants and the reaction conditions, dinuclear, trinuclear, and tetranuclear compounds, [Mn(2)(t-BuPO(3)H)(4)(phen)(2)]·2DMF (1), [Mn(3)(C(5)H(9)PO(3))(2)(phen)(6)](ClO(4))(2)·7CH(3)OH (2), [Mn(3)(t-BuPO(3))(2)(dpzpy)(3)](ClO(4))(2)·H(2)O (3), [Mn(4)(t-BuPO(3))(2)(t-BuPO(3)H)(2)(phen)(6)(H(2)O)(2)](ClO(4))(2) (4), and [Mn(4)(C(5)H(9)PO(3))(2)(phen)(8)(H(2)O)(2)](ClO(4))(4) (5). Magnetic studies on 1, 2, and 4 reveal that the phosphonate bridges mediate weak antiferromagnetic interactions between the Mn(II) ions have also been carried out.     

Syntheses and Crystal Structure of Erbium(Ⅲ) Coordination Polymers with Two Flexible Double Betaine Ligands

1INTR0DUCTI0NLanthanidecarboxylatecomplexeshavebeenwidelystudiedt1iandm0starefoundtoexhibitavarietyofdimericorinfinitechainstructures.Recentstudiesinourlaboratoryhavedem0nstratedthattheprototypetertiaryaminebetaine(Me,N CHzC0z-)anditsderivativesareusefulinthegenerationoflanthanidecarb0xylate-likecomplexeswithnewstructuralfeaturesduetotheiroverallchargeneutralityandpossibleinclusionofvariouskindsofcounteranionsinthestructuret2~4i.Thelan-thanidecomplexesisolatedsofarhavebeenfoundtobemononu…     

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.     

Coordination Polymers with Bipyridyl Diene and Triene Ligands: Synthesis,Structures and Luminescent Properties

Solvothermal reactions of cadmium salts with bipyridyl diene and triene ligands[1,3-bis((E)-2-(pyridin-4-yl)vinyl)benzene-(1,3-bpeb) and 1,6-bis(4-pyridyl)-1,3,5-hexatriene(bphte)] and one bipyridyl triene ligand[1,6-bis(4-pyridyl)-1,3,5-hexatriene-(bphte)] in the presence of auxiliary carboxylic acids including 2,6-dichlorobenzoic acid(2,6-HDCBA) and 2-naphthal-enecarboxylic acid(2-HNCA) gave rise to four coordination polymers[Cd(bphte)(2,6-DCBA)₂]_n(1), {[Cd(bphte)(2-NCA)₂]·5.8H₂O}_n(2),[Cd₂(1,3-bpeb)₂(2,6-DCBA)₄]_n(3) and {[Cd₄(1,3-bpeb)₄(2-NCA)₇(HCOO)]·     

由双核铜簇与柔性双三氮唑基配体构筑的一维链状铜配合物的合成、结构与光学性质表征

基于柔性的双三氮唑基配体和刚性的芳香羧酸,合成得到了一个一维链状铜配位聚合物[Cu2(bza)4(btx)]n(1)(btx=1,4-二(1,2,4-三唑基-1-基甲基)苯,Hbza=苯甲酸),并通过元素分析、红外光谱、X-射线单晶衍射、热分析、荧光光谱等测试对其进行了表征。晶体数据表明该化合物属于三斜晶系,P1空间群。在化合物1中,羧酸根均采取双齿桥联的模式,4个苯甲酸配体螯合2个铜离子构成1个双核铜单元(Cu-Cu键的距离为0.26 nm),这些双核铜单元又通过柔性双三氮唑基配体桥联形成一维链状的结构;热分析表明该化合物具有相对较高的热稳定性,室温下的固态荧光测试发现,在398 nm激发下,化合物1发射出绿色光。     

含有微孔结构的吡啶二羧酸金属锰配位聚合物(英文)

<正>0 Introduction The realm of crystal engineering has provided a sound junction between aesthetics of crystalline architectures[1-2]and their potential functions[3-4],of which the ultimate destination is to successfully achieve     

Structure Modulation in Four New Coordination Polymers by In Situ Ligands Synthesis of Anthracene Derivatives and Various Auxiliary N-donor Ligands

Four novel coordination polymers, [Zn(HL¹)₂(phen)₂]·2CH₃OH·2H₂O (1), [ZnCl(HL¹)(4,4′-bipy)_0.5] _n (2), [Cd(HL¹)(L²)_0.5(2,2′-bipy)₂]·3H₂O (3), [Zn(L³)_0.5(N₃)_1.5(phen)] _n (4) (H₂L¹ = 9-(1H-tetrazole-5-yl)-10-carboxyl anthracene, H₂L² = 9,10-di-(1H-tetrazole-5-yl) anthracene, HL³ = 9-(1H-tetrazole-5-yl)-10-cyan anthracene, 1,10-phen = 1,10-phenanthroline, 4,4′-bipy = 4,4′-bipyridine, 2,2′-bipy = 2,2′-bipyridine), have been constructed by in situ ligands synthesis system. The formation of tetrazole-based ligands H₂L¹, H₂L² and H₂L³ involves the in situ Sharpless [2 + 3] cycloaddition reaction between 9,10-dicyanoanthracene (DCA) and NaN₃ in the presence of Zn²⁺/Cd²⁺ ions as Lewis-acid catalysts under hydro/solvothermal conditions. At the same time, there is also another in situ carboxyl ligand synthesis reaction by hydrolysis from nitrile in compounds 1 and 2. The four compounds have been characterized by elemental analysis, IR and single-crystal X-ray diffraction analysis. Compound 1 exhibits a butterfly-shaped mononuclear structure. Compound 2 represents a 2D framework constructed by six-membered {Zn₆} rings as secondary building units (SBUs). Compound 3 presents a dinuclear {Cd₂} structure with two butterflies “flying side by side” fashion. While compound 4 displays a 1D chain structure based on a dinuclear {Zn₂} SBUs. Moreover, the luminescence properties of 1–4 have been also investigated.     

Synthesis,Structure, and Luminescent Properties of Lanthanide Coordination Polymers Based on 5‐Hydroxyisophthalate and Phen Ligands

Three lanthanide coordination polymers incorporating 5‐hydroxyisophthalate ( L ) and phen ligands, [Eu( L )(phen)]_n ( 1 ) and [Ln( L )(phen)₂]_n [Ln = Sm ( 2 ) and Pr ( 3 )], were synthesized. X‐ray structural analysis reveals that 1 features a (3,6)‐connected 3D rtl topology. Complexes 2 and 3 are isostructural and have 2D sheets with 6³ topology. Comparison of the structural differences between 1 and 2 (or 3 ) suggests that the different metal sources play an important role in the formation of such coordination networks. Compounds 1 and 2 show photoluminescence and their emission properties are closely related to their corresponding central Ln^III atoms.     

新型手性金属-有机配位聚合物的合成、结构与性质

在水热条件下, 分别用过渡金属离子Zn(Ⅱ)和Co(Ⅱ)与混合手性羧酸和含氮配体反应, 合成了2个手性金属-有机配位聚合物[M(D-cam)(H₂mbdpz)]_n[M=Zn(1), Co(2); D-H₂cam=D-(+)-樟脑酸; H₂mbdpz=4,4'-亚甲基二(3,5-二甲基吡唑)]. 通过单晶X射线衍射、粉末X射线衍射、元素分析、热重分析及荧光分析对其结构、组成和性质进行了表征. 单晶结构分析表明, 配合物1和2是异质同晶的手性三维开放骨架结构, 具有单节点三连接的ThSi₂型网络拓扑结构.     

Coordination Polymers of Ni(II) with Thiophene Ligands: Synthesis,Structures, and Magnetic Properties

Russian Journal of Coordination Chemistry - Two new metal-organic frameworks [Ni(btdc)(bipy)(H2O)2] (I) and [Ni(azobipy)(H2O)4](btdc) (II) (H2btdc is 2,2'-bithiophene-5,5'-dicarboxylic...     

Transition Metal Ion-Directed Coordination Polymers with Mixed Ligands: Synthesis,Structure, and Photocatalytic Activity for Hydrogen Production and Rhodamine B Degradation

Three mixed-ligand transition metal coordination polymers with the formula of {[Cu^I₂Cu^II(tpt)₂(L)] · 15H₂O}_n ( 1 ) and {[M₂(H₂O)₅(tpt)(L)] · 6H₂O}_n [M = Ni for 2 and Co for 3 ; tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine and L = 3,3'-disulfonyl-4,4'-biphenyldicarboxylate] were hydrothermally synthesized by varying the cheap paramagnetic metal ions and used as photocatalysts for hydrogen evolution from water splitting and rhodamine B (RhB) degradation. Single-crystal structural determinations reveal that 1 is a robust pillared-layer framework with unusual 72-membered {Cu₆(tpt)₆} macrocycle-based layers supported by tetratopic L^4– connectors. Both 2 and 3 are isostructural (4 4) sheets with octahedral Ni^II and Co^II ions extended by ditopic L^4– and tpt linkages, in which the third pyridyl group of tpt is capped by pentahydrated metal ions. Due to the narrowed bandgap and good charge transport of the mixed-valence Cu^I/II centers, 1 exhibits improved dual-functional catalytic activities than 2 and 3 with the visible-light-driven hydrogen evolution rate and RhB degradation efficiency up to 588 μmol · g^–1 · h^–1 and 72 % after 180-minute irradiation. These interesting results indicate the importance of the metal ions and the dimensionality of the coordination polymers on the activity of the non-Pt coordination polymer photocatalytic systems.     

Two Novel Coordination Polymers of Schiff Base Ligands: Synthesis,Crystal Structures and Antibacterial Properties Studies

Two novel complexes [Ag L~1(NO_3)H_2O]_n(1) and [Pb L_2(NO_3)_2]_n(2) were synthesized by the evaporation reaction with metal salts and Schiff base ligands. They were characterized by elemental analyses, IR spectra and X-ray single-crystal diffraction. 1 crystallizes in monoclinic, space group P21/c with a = 18.358(3), b = 10.0395(15), c = 13.4643(16) ?, β = 91.749(12)o, V = 2480.4(6) ?3, Dc = 1.597 g/cm~3, Mr = 596.35, F(000) = 1208, Z = 4, R = 0.0772 and w R = 0.0927. 2 crystallizes in monoclinic space group C2/c with a = 15.8549(10), b = 21.1988(17), c = 17.7198(12) ?, β = 105.829(8)o, V = 5729.9(7) ?~3, Dc = 1.645 g/cm~3, Mr = 709.63, F(000) = 2736, Z = 8, R = 0.0541 and w R = 0.1175. X-ray single-crystal diffraction experiments of 1 and 2 display that extensive π×××π stacking interactions and hydrogen bonds construct into a 2D rectangular network and a 3D supramolecular framework. The antibacterial properties of L1, L2, 1 and 2 were also studied.     

四个Cd(Ⅱ)配位聚合物:辅助配体对晶体结构以及荧光性能的影响

采用溶剂热的方法,将配位模式丰富的多羧酸有机配体5-(2-硝基-4-羧基苯氧基)-间苯二甲酸(H3ncpoi)与Cd~(2+)离子以及不同的辅助配体原位组装而成4个新的配位聚合物晶体:[Cd(Hncpoi)(2,2′-bpy)(H2O)]n(1),{[Cd2(Hncpoi)2(bpyp)(H2O)4]·3H2O}n(2),{[Cd2(Hncpoi)2(azpy)(H2O)2]·2H2O}n(3),{[Cd2(Hncpoi)2(dpe)(H2O)2]·2H2O}n(4),其中H3ncpoi为5-(2-硝基-4-羧基苯氧基)-间苯二甲酸,2,2′-bpy为2,2′-联吡啶,bpyp为1,4-二-吡啶基-4-亚甲基-哌嗪,azpy为4,4′-偶氮吡啶,dpe为1,2-二-(4-吡啶基)乙烯。对4个配合物进行了X射线单晶衍射、粉末衍射,元素分析、热重、荧光光谱等表征。X射线单晶结构分析表明,配合物1,2具有一维链状结构,而配合物3,4则具有二维(4,4)格子层状结构,一维链和二维层之间通过分子间作用力连接成三维超分子结构。进一步研究表明,辅助配体的构型、配位方式等对晶体结构具有决定性作用。与此同时,对几个配合物的荧光光谱进行分析,发现不同的辅助配体对配合物的荧光性能有着显著的影响。     

4个Cd(Ⅱ)配位聚合物:辅助配体对晶体结构以及荧光性能的影响

采用溶剂热的方法,将配位模式丰富的多羧酸有机配体5-（2-硝基-4-羧基苯氧基）-间苯二甲酸（H₃ncpoi）与Cd²⁺离子以及不同的辅助配体原位组装而成4个新的配位聚合物晶体：[Cd（Hncpoi）（2,2''-bpy）（H₂O）]_n（1）,{[Cd₂（Hncpoi）₂（bpyp）（H₂O）₄]·3H₂O}_n（2）,{[Cd₂（Hncpoi）₂（azpy）（H₂O）₂]·2H₂O}_n（3）,{[Cd₂（Hncpoi）₂（dpe）（H₂O）₂]·2H₂O}_n（4）,其中H₃ncpoi为5-（2-硝基-4-羧基苯氧基）-间苯二甲酸,2,2''-bpy为2,2''-联吡啶,bpyp为1,4-二-吡啶基-4-亚甲基-哌嗪,azpy为4,4''-偶氮吡啶,dpe为1,2-二-（4-吡啶基）乙烯。对4个配合物进行了X射线单晶衍射、粉末衍射,元素分析、热重、荧光光谱等表征。X射线单晶结构分析表明,配合物1,2具有一维链状结构,而配合物3,4则具有二维（4,4）格子层状结构,一维链和二维层之间通过分子间作用力连接成三维超分子结构。进一步研究表明,辅助配体的构型、配位方式等对晶体结构具有决定性作用。与此同时,对几个配合物的荧光光谱进行分析,发现不同的辅助配体对配合物的荧光性能有着显著的影响。     

Synthesis of Coordination Polymers Using Different Maleic Acid Ligands under Hydrothermal Conditions

A novel coordination polymer, [Ni(mal)(1,10′-phen)(H2O)]n(1)(mal=malate, 1,10′-phen=1,10-phenanthroline) was synthesized using malic acid which was generated from maleic acid via hydrothermal reaction. Complex 1, which displays a two-dimensional supramolecular network, was formed by the addition reaction of Ni and maleic acid with water molecules. To our knowledge, several coordination polymers have been directly synthesized from malic acid, but these types of complexes have seldom been synthesized from maleic acid via hydrothermal reactions. When Ni(Ⅱ) ion was changed to Zn(Ⅱ) ion under the same condition, two-dimensional covalent complex 2[Zn2(fma)2(1,10′-phen)2]n(fma=fumatic acid) was formed. Furthermore, complex 2 exhibits intense photoluminescent property at room temperature.     

Schiff碱双核Mn配合物的合成、结构和性能研究

Five manganese complexes of Schiff base were synthesized： [Mn^Ⅳ，Ⅳ(μ-O)(Salen)]₂·DMF·H₂O (1)， [Mn^Ⅳ，Ⅳ(μ-O)(5-BrSalen)]₂·DMF·0.5H₂O (2)， {Mn^Ⅳ，Ⅳ(μ-O)[Sal(1，2-pn)]}₂·H₂O (3)， {Mn^Ⅳ，Ⅳ(μ-O)[5-Br-Sal(1，2-pn)]}₂·H₂O (4)， {Mn^Ⅳ，Ⅳ(μ-O)[5-CH₃-Sal(1，2-pn)]}₂·2H₂O (5)， and were characterized by element analysis， IR and UV-Vis spectra. The results of cyclic voltammogram show that Schiff base ligands can drop the potential of manganese and steady high oxide state of manganese. The magnetic properties of 1 and 3 have also been studied. The results show that there is a weak ferromagnetically coupling of Mn^Ⅳ₂ pair at room and low temperature， and the interactions of complex 3 are weaker than complex 1.     

Hydrothermal Synthesis of Two New Transition Metal Coordination Polymers with Mixed Ligands

Hydrothermal reactions of 1, 2, 4‐benzenetricarboxylic acid, 1, 10‐phenanthroline and transition metal cations including Zn^II or Co^II, in basified aqueous solution gave rise to two complexes, [Zn₃(btrc)₂(1, 10‐phen)₂(H₂O)₂]_n ( 1 ), and [Co₃(btrc)₂(1, 10‐phen)₂(H₂O)₂]_n ( 2 ) (btrc = 1, 2, 4‐benzenetricarboxylate, and 1, 10‐phen = 1, 10‐phenanthroline). 1 2 crystalize isotypically in the triclinic space group P1¯. The btrc ligand acts as multi‐dentate bridging ligand in both compound 1 and 2 to link up transition metal atoms into lamella networks, which are further attached into three‐dimensional frameworks through complex hydrogen bonding and π‐π interactions. The photoluminescence spectrum for compound 1 has also been studied. The corresponding reaction with Cu²⁺ follows another pathway.