Synthesis,Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn （NAA ）2（ 4,4′-bipy ） （H2O）4]n

A novel one-dimensional chain coordination polymer [Mn（NAAh（4,4′-bipy）（H2O）4], has been synthesized with a-naphthaleneacetic acid, 4,4′-bipy and manganese（Ⅱ） sulfate as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1421（2）, b = 1.6337（3）, c = 0.94177（19） nm, β = 112.15（3）°, V = 1.6275（6） nm^3, De = 1.407 g/cm^3, Z = 2, μ（MoKa） = 0.467 mm^-1, F（000） = 722, S = 1.007, R= 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese（Ⅱ） ions are linked together by one 4,4′-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese（Ⅱ） ion is coordinated with two oxygen atoms of two a-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4′-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.     

一维链状锰配位聚合物[Mn(3,5-Me2PhCO2)2(phen)]n的合成与晶体结构

A manganese coordination polymer [Mn(3,5-Me₂PhCO₂)₂(phen)]_n(phen=1,10-phenanthroline) has been synthesized by hydrothermal methods. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a=0.770 3(4) nm, b=1.145 2(6) nm, c=1.537 0(9) nm, α=78.182(9)°, β=77.170(9)°, γ=89.784(9)°, V=1.292 8(12) nm³, Z=2, M_r=533.47, D_c=1.370 g·cm^-3, μ=0.549 mm^-1, F(000)=554, R_int=0.043 4, R=0.060 8 ,wR=0.148 4. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from phen and four oxygen atoms from four 3,5-dimethylbenzolate molecules, completing an octahedral geometry. And the title complex forms one-dimensional chain structure through bridging 3,5-dimethylbenzolate molecules. CCDC: 642920.     

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4''-bipy)(H2O)5]n

A one-dimensional chain coordination polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4'-bipy)(H2O)5]n has been synthesized with cinnamylic acid, 4,4'-bipy and cobaltous chloride as raw materials. Crystal data for this complex: monoclinic, space group P21/c, a - 1.1481(3), b =1.1230(2), c = 1.1759(3) nm, β = 97.054(4)°, V = 1.5046(6) nm3, Mr= 617.50, Dc = 1.363 g/cm3, Z= 2, μ(MoKα) = 0.627 mm-1, F(000) = 646, S = 1.062, R 0.0443 and wR = 0.1178. The crystal structure shows that two neighboring cobalt(Ⅱ) ions are linked together by one 4,4'-bipy, and the whole complex molecule adopts a one-dimensional chain structure. Each cobalt(Ⅱ) ion is coordinated with two nitrogen atoms from two 4,4'-bipy molecules and four oxygen atoms from four water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were analyzed by combining with the crystal structure.     

配合物[Mn(2,2''-bipy)(H2O)4]·(m-phth)的水热合成和晶体结构

A mononuclear manganese complex [Mn(2,2'-bipy)(H2O)4]·(m-phth) (2,2'-bipy=2,2'-bipyridine, m-phth=isophthalate) has been synthesized by hydrothermal methods. The crystal structure was determined by singlecrystal X-ray diffraction. The crystal is of orthorhombic, space group Pnna with a=0.766 8(8) nm, b =2.050 2(2)0.027 0, R=0.028 0 and wR=0.075 5. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from 2,2'-bipyradine and four oxygen atoms from water molecules, completing an octahedral coordination geometry. The isophthalate molecules are included in the lattice and connected to Mn(2,2'-bipy)(H2O)4 by hydrogen bonding interactions to form a three-dimensional supramolecular structure. CCDC:286965.     

2，2-联吡啶-3，3-二羧酸桥联的具有2D网格结构的Mn配位聚合物的合成、晶体结构

A Manganese(Ⅱ) polymer {[Mn(bpdc)(bipy)(H₂O)]·4.5H₂O}_n has been synthesized (bpdc=2,2-bipyridine-3,3-dicarboxylate,bipy=4,4-bipyridine) and characterized by IR, UV, elemental analysis and X-ray crystal structure determination . It crystallizes in Monoclinic system, space group P2/n with a=1.010 13(8) nm, b=1.164 66(9) nm, c=2.147 40(16) nm, β=98.22 20(10)°, V=2.500 4(3) nm³, Z=4, D_c=1.467 g·cm^-3, F(000)=1 144, R₁=0.049 0, wR₂=0.141 2. The crystal structure shows that the Mn²⁺ ions have octahedral coordination geometry with two coordination situations. The Mn²⁺ (1) ion is coordinated with two N atoms of two bipy, and chelated by four O atoms from four carboxylate groups of two bpdc ligands. The neighbor Mn²⁺ (2) ion is coordinated with two oxygen atoms from two water, two N atoms of two 4,4-bipy and two O atoms from two carboxylate groups of two bpdc ligands. Mn(1) and Mn(2) ions are bridged by bpdc and bipy ligands, forming a novel 2D network. CCDC: 651043.     

[Zn2(C7H8O6)2(bipy)2(H2O)2]·4H2O手性配位聚合物的合成与晶体结构

采用溶剂热技术合成了一种新型手性配位聚合物[Zn2(C7H8O6)2(bipy)2(H2O)2]·4H2O(C7H8O6=2,3-氧-异丙叉基-L-酒石酸根, bipy=4,4'-联吡啶), 并通过单晶X射线衍射结构分析、元素分析、热重分析以及红外光谱进行了表征. 结构分析数据表明, 该化合物属单斜晶系, C2空间群, 晶胞参数a=2.02334(14) nm, b=1.13896(4) nm, c=1.01094(6) nm, β=117.366(3)°, V=2.0689(2) nm3. 两个晶体学独立的Zn原子均为八面体构型, 其中Zn1原子赤道配位点被2个酒石酸根中的4个羧酸根氧螯合配位, 2个酒石酸根中剩下的4个羧酸根氧中的2个分别与2个Zn2原子连接形成无限一维链, Zn2原子的另外2个反式赤道配位点被2个水分子氧占据, 同时这两种Zn原子的轴向配位点均被4,4'-联吡啶的氮原子占据, 形成具有矩形格子[0.51165(3) nm×1.13896(5) nm]的二维层状结构, 游离的2个水分子通过氢键作用形成二聚体, 并与酒石酸根中未与Zn配位的羧酸氧连接, 把二维层状结构连接成三维网状的超分子结构.     

一维链状锰配合物的合成、结构及磁性研究

合成了邻硝基苯磺酰化丙氨酸配体2-NBS-AlaH (1)(2-NBS-AlaH=邻硝基苯磺酰化丙氨酸)及其锰的配合物[Mn(4，4′-bipy)(H₂O)₄]₂[(4，4′-bipy)₂(H₂O)₃(2-NBS-Ala)₄] (2)。通过X-射线单晶衍射测定了其结构：配体通过氢键形成了一维链状结构；配合物2中，4，4′-bipy把锰离子连成了一维链状结构。磁性研究表明，配合物由于分子间的自旋耦合呈现出弱的铁磁性。     

一维链状3-碘苯甲酸铽配合物的合成、晶体结构和性质表征

溶液法合成了配合物{[Tb(3-IBA)₃(H₂O)₂]·0.5(4,4′-bipy)}_n(3-IBA=3-碘苯甲酸根;4,4′-bipy=4,4′-联吡啶),并通过X-射线衍射单晶结构分析、红外光谱、紫外光谱、荧光光谱以及热重分析对配合物进行了结构和性质表征。配合物晶体属三斜晶系,P1空间群。该配合物具有一维链状结构。Tb³⁺离子与8个O原子配位,其中6个O原子来自5个3-碘苯甲酸根,2个O原子来自水分子。相邻Tb³⁺离子通过2个双齿桥联的3-碘苯甲酸根联结成一维链状结构。未配位的4,4′-联吡啶分子与配位水分子之间形成氢键,并将相邻的一维链联结起来形成二维网状结构。沿a轴的分子堆积形成一维孔道,是由于相邻一维链的苯环之间部分重叠而形成的。在紫外光照射下,配合物发出很强的绿色荧光。配合物的荧光光谱中,4个峰位于490、544、583和619 nm,分别对应于Tb³⁺离子的⁵D₄→⁷F₆、⁵D₄→⁷F₅、⁵D₄→⁷F₄和⁵D₄→⁷F₃跃迁。     

Syntheses, structures, and properties of five coordination polymers containing fluorescent whitener

Fluorescent whitener (4,4'-bis(2-sulfonatostiryl)biphenyl) was incorporated with M/4,4'-bipy (M=Cd, Co; 4,4'-bipy=4,4'-bipyridine) 2D frameworks, Mn/4,4'-bipyH fragment, and the [Zn2(Im)2(ImH)4]2+ (ImH=imidazole) chain under hydrothermal conditions to obtain seven new coordination polymers: [Cd(4,4'-bipy)(L)(H2O)2] (1), [Co(4,4'-bipy)2(L)].2H2O (2), [Co(4,4'-bipy)2(H2O)2](4,4'-bipy)(L).2H2O (3), [Mn(4,4'-bipyH)2(L)2(H2O)2].4H2O (4), and [Zn2(Im)2(ImH)4](L) (5). Their structures were determined by single-crystal X-ray diffraction. In 1, binuclear [Cd2] units are bridged by 4,4'-bipys into a 2D cationic framework, which is further penetrated by L anions. 2 has an organic-inorganic hybrid layer consisting of [Co(4,4'-bipy)2] squarelike motifs and L anions. 3 features a pcu-like 3D cationic framework with the inclusion of L anions. In 4, the [Mn(4,4'-bipyH)2(H2O)2]4+ cationic fragment is sandwiched by L anions into a sandwichlike hybrid layer. 5 exhibits a 3D honeycomb-like structure with each nanotube encapsulating two parallel L anionic chains. TGA and PXRD indicate solids 1, 4, and 5 are thermally stable up to 280, 200, and 250 degrees C under an air atmosphere, respectively. 1 has bright blue-green luminescence with a peak maximum band at about 470 nm. 4 exhibits tunable emission between dark-red and weak-green under the excitation of 500 and 280 nm, respectively. 5 displays a bright blue-green emission with a peak band at 454 nm and a shoulder peak at 473 nm. It is attractive that the luminescent properties of solids 1, 4, and 5 are almost retained after heat treatment at 200, 200, and 250 degrees C for 2 h under an air atmosphere, respectively.     

Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn2(HCAM)3(H2bipy)]·5H2O}n

The 1-D chain coordination complex of {[Mn2(HCAM)3(H2bipy)]·5H2O}n(H3CAM=4-hydroxypyridine-2,6-dicarboxylic acid,bipy=4,4′-bipyridine) has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid,4,4′-bipyridine and manganese carbonate under hydrothermal conditions,and its crystal structure was determined by X-ray diffraction method.The crystal belongs to the monoclinic system,space group P21/n with a=10.110(2),b=20.159(4),c=17.861(4) ,β=99.67(3)°,V=3.5884(12) nm3,Mr=901.47,Z=4,Dc=1.669 g·cm-3,μ=0.798 mm-1,F(000)=1840,the final R=0.0713 and wR=0.1853.The complex forms a 1-D chain bridged by HCAM,protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H…O hydrogen bonds,and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.     

配位聚合物[Mn(4，4′-bpy)1.5(H2O)3](ClO4)·(4，4′-bpy)(L)·H2O的水热合成和晶体结构

The title compound, [Mn(4,4′-bpy)_1.5(H₂O)₃](ClO₄)·(4,4′-bpy)(L)·H₂O(1), where L=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 0(1) nm, α=105.300(2)°, β=97.495(2)°, γ=91.118(2)°, V=1.884 0(4) nm³, Z=2, M_r=780.10, D_c=1.375 g·cm^-3, μ=0.483 mm^-1, F(000)=812, R=0.055 4, wR=0.135 2. The Mn atoms are octahedrally coordinated by three N atoms of three 4,4′-bipyridine ligands and three O atoms of water. The complex shows a one-dimensional chain structure bridged by water and 4,4′-bipyridine molecules. CCDC: 615707.     

一维链状配位聚合物[Cd{5-(NO2)sal}2(2,2'-bipy)]n的合成与晶体结构

A coordination polymer of [Cd{5-(NO2)sal}2(2,2'-bipy)]n (5-(NO2)sal=5-nitrosalicylate, 2,2'-bipy=2,2'-bipyridine) was synthesized by hydrothermal reaction and characterized by elemental analysis, IR and X-raydiffraction single crystal structure analysis. The title complex crystallizes in monoelinic with space group C2/c, a=2.730 8(16) nm, b=1.272 3(5) nm, c=0.674 5(3) nm,β=96.73(2)°, V=2.327(2) nm3, Z=4, R=0.022 2, wR=0.057.The 5-nitrosalicylate anions doubly bridge the Cd(Ⅱ) atoms to form one-dimensional polymeric chain with therepeated eight-membered ring units (Cd-O-C-O)2. The crystal structure is stabilized by intra- and interchainhydrogen bonds interactions.     

Hydrothermal Synthesis and Crystal Structure of a One-dimensional Manganese(Ⅱ) Compound Bridged by 2,6-Dichlorobenzoic Acid and Water

A novel manganese(Ⅱ) coordination polymer [Mn(L1)2(H2O)]·2H2O (HL1 = 2,6-dichlorobenzoic acid) 1 has been synthesized and structurally characterized.X-ray diffraction analyses reveal that 1 is a one-dimensional chain structure bridged by water molecules and 2,6-dichlorobenzoic acid.The crystal is of monoclinic,space group P21/c with a = 12.9701(19),b =20.592(3),c = 7.3759(10) (A),β = 102.660(2)°,V = 1.9221(5) nm3,Z = 4,C14H12Cl4MnO7,Mr=488.98,Dc = 1.690 g/cm3,μ = 1.275 mm-1,F(000) = 980,Rint = 0.0348,R = 0.0350,and wR =0.0755.In the crystal the manganese atom is six-coordinated by two oxygen atoms from water and four oxygen atoms from four 2,6-dichlorobenzolate molecules,completing an octahedral geometry.     

Crystal Structure and Magnetic Property of a Two-dimensional Manganese Compound [Mn(PhCOO)_2(4,4'-bipyridine)]_n

A new two-dimensional polymeric manganese compound [Mn(PhCOO)2(4,4'-bi-pyridine)]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158(2), b = 11.6919(3), c = 9.4799(2) , V = 2074.42(7) 3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm3, μ = 0.670 mm-1 and F(000) = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with I > 2σ(I). The complex consists of repeating units of Mn(PhCOO)2(4,4'-bipyridine). Each Mn center is six-coordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.     

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn(NAA)_2(4,4’-bipy)(H_2O)_4]_n

A novel one-dimensional chain coordination polymer [Mn(NAA)2(4,4’-bipy)(H2O)4]n has been synthesized with α-naphthaleneacetic acid, 4,4’-bipy and manganese(II) sulfate as raw ma-terials. Crystal data for this complex: monoclinic, space group P21/c, a = 1.1421(2), b = 1.6337(3), c = 0.94177(19) nm, β = 112.15(3)o, V = 1.6275(6) nm3, Dc = 1.407 g/cm3, Z = 2, μ(MoKα) = 0.467 mm-1, F(000) = 722, S = 1.007, R = 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese(II) ions are linked together by one 4,4?-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese(II) ion is coordinated with two oxygen atoms of two α-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4?-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.     

Crystal Structure and Magnetic Property of a Two-dimensional Manganese Compound [Mn（PhCOO）2（4,4＇-bipyridine）]n

A new two-dimensional polymeric manganese compound [Mn(PhCOO)2(4,4'-bipyridine)]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158(2), b = 11.6919(3), c = 9.4799(2)(A), V = 2074.42(7)(A)3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm3, μ = 0.670 mm-1 and F(000) = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with Ⅰ＞ 2σ(Ⅰ). The complex consists of repeating units of Mn(PhCOO)2(4,4'-bipyridine). Each Mn center is sixcoordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.     

Hydrothermal Syntheses and Crystal Structures of Two Complexes with 3,5- Dinitrosalicylate and 2,2′-Bipyridine Ligands

The two title complexes,[Cd{3,5-(NO2)2sal}(2,2′-bipy)]n 1 and [Mn{3,5-(NO2)2sal}(2,2′-bipy)]n 2 (3,5-(NO2)2sal=3,5-dinitrosalicylate,2,2′-bipy=2,2′-bipyridine),were synthesized by the hydrothermal reaction and structurally characterized. Complex 1 crystallizes in triclinic,space group P1,a=5.581(4),b=12.071(8),c=12.88(1),α=92.10(3),β=96.73(3),γ =102.02(2)°,C17H10N4O7Cd,Mr=494.69,V=841(1)3,Z=2,Dc=1.954 g/cm3,F(000)=488,μ =1.353 mm-1,R=0.0248 and wR=0.0761. Complex 2 crystallizes in monoclinic with space group P21/c,a=8.604(3),b=23.88(1),c=8.894(3),β=102.45(1)°,C17H10N4O7Mn,Mr=437.23,V= 1785(1) 3,Z=4,Dc=1.627 g/cm3,F(000)=884,μ=0.791 mm-1,R=0.0471 and wR=0.1250. Complex 1 possesses an infinite 1D polymeric chain structure consisting of the repeated basic four-membered ring units (Cd2O2) and eight-membered ring units (CdOCO)2. Compound 2 displays a linear 1D chain through Mn(Ⅱ) atoms and bridging carboxylate groups of 3,5-dinitrosalicylic acid ligands with the Mn…Mn separation of 4.472(2). The fluorescence properties and cyclic voltammetric behaviors of the complexes are also reported.     

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co(II)(C_6H_5CH=CHCOOH)_2(4,4′-bipy)(H_2O)_5]_n

A one-dimensional chain coordination polymer [Co(II)(C6H5CH=CHCOOH)2(4,4′- bipy)(H2O)5]n has been synthesized with cinnamylic acid, 4,4′-bipy and cobaltous chloride as raw materials. Crystal data for this complex: monoclinic, space group P21/c, a = 1.1481(3), b = 1.1230(2), c = 1.1759(3) nm, β = 97.054(4)o, V = 1.5046(6) nm3, Mr= 617.50, Dc = 1.363 g/cm3, Z = 2, μ(MoKα) = 0.627 mm-1, F(000) = 646, S = 1.062, R 0.0443 and wR = 0.1178. The crystal structure shows that two neighboring cobalt(II) ions are linked together by one 4,4′-bipy, and the whole complex molecule adopts a one-dimensional chain structure. Each cobalt(II) ion is coordinated with two nitrogen atoms from two 4,4′-bipy molecules and four oxygen atoms from four water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were analyzed by combining with the crystal structure.     

环己烷甲酸根桥联的二维锰配合物的合成与表征

Complex [Mn₂(C₆H₁₁CO₂)₃(4,4′-bipy)₂(H₂O)₂]ClO₄ (C₆H₁₁CO₂H=cyclohexanecarboxylic acid) was synthesized by reaction of Mn(ClO₄)₂·6H₂O, C₆H₁₁CO₂Na and 4,4′-bipy in methanol. The title complex crystallizes in triclinic space group P1, with a=1.008 8(2) nm, b=1.086 3(1) nm, c=1.164 9(3) nm, α=63.016(3)°, β=81.998(4)°, γ=88.604(1)°, V=1.125 4(4) nm³, Z=1. There are two types of Mn atoms in the structure with each in octahedral geometry. Mn1 and Mn2 are bridged by cyclohexanecarboxylate ligands into a chain and the chains are further linked together by 4,4′-bipy into a 2D plane. CCDC: 692247.     

Hydrothermal synthesis, crystal structure, conductivity, and thermal decomposition of [Cu(4,4'-bipy)(H2O)(Mo3O10)].H2O

The hydrothermal reaction of (NH(4))(6)Mo(7)O(24).4H(2)O, CuCl(2).2H(2)O, and 4,4'-bipyridine yields bipyridine-ligated copper-trimolybdate monohydrate [Cu(4,4'-bipy)(H(2)O)(Mo(3)O(10))].H(2)O in the monoclinic system with space group of C(2/c) and cell parameters of a = 15.335(2) A, b = 15.535(2) A, c = 15.106(2) A, beta = 101.162(2) degrees, V = 3530.7(9) A(3), and Z = 8. Its structure consists of one-dimensional infinite ([Mo3O10]2-)( infinity ) chains linked through [Cu2(H2O)2(4,4'-bipy)] units. The Mo-O chain contains distorted [MoO(6)] octahedra connected through corner-sharing oxygen atoms into infinite chains along the c direction and each chain is located in the channel formed by four adjacent crossing chains of [Cu(4,4'-bipy)(H2O)](n)(2n+). The crystal shows weak conductivity through Mo-O chain along the c direction and insulating property along either a or b direction. Furthermore, a crystalline bimetallic oxide, CuMo3O10, forms when the title compound undergoes thermal treatment in N(2) atmosphere after the complete removal of the ligands.