Solvothermal Synthesis, Crystal Structure and Luminescent Property of a Dy（Ⅲ） Coordination Polymer Constructed by 1,2,4,5-Benzenetetracarboxylic Acid

A three-dimensional coordination polymer {[Dy(H2btec)2/4(btec)3/6(H2O)]·2H2O} n has been synthesized through the reaction of DyCl3·6H2O and 1,2,4,5-benzenetetracarboxylic acid by solvothermal technique, and the crystal structure was determined by X-ray diffraction. The Dy(Ⅲ) coordination polymer crystallizes in monoclinic, space group P21/n with a=10.7063(1), b=7.1491(1), c=17.1197(3), α=90, β=97.10, γ=90°, V=1300.31(3)3 , C10H9DyO11 , Dc=2.389g/cm3 , Z=4, F(000)=892, the final R=0.0165 and wR=0.0448 for I > 2σ(I). The title coordination polymer possesses a three-dimensional framework consisting of nine-coordinate Dy(Ⅲ) centers and two kinds of coordination modes for the 1,2,4,5-benzenetetracarboxylic acid ligands. Every btec4- ligand (deprotonated four protons from 1,2,4,5-benzenetetracarboxylic acid) in the title coordination polymer can clamp three Dy atoms like forceps, which could make the Dy atoms closer in the area of metal-metal interaction. The 3-D framework of the coordination polymer has many channels occupied by the free guest water molecules, and the hydrogen bonds between the coordinated carboxylic groups and guest water molecules could stabilize the crystal structure of the title coordination polymer. In addition, the luminescence properties were also studied.     

Syntheses and characterizations of copper(II) polymeric complexes constructed from 1,2,4,5-benzenetetracarboxylic acid

Four polymeric complexes with rectangular grids or channels, [Cu2(btec)(H2O)4*2H2O]n (2), [Cu2(btec)4/4[Cu(Hbtec)2/2(4,4'-Hbpy)(H2O)2]2*4H2O]n (3), [Cu2(btec)(hmt)(H2O)4*8H2O]n (4), and [Cu3(btec)(OH)2]n (5), were designed and constructed from Cu(II) ion and 1,2,4,5-benzenetetracarboxylic acid along with auxiliary ligands (where H4btec = 1,2,4,5-benzenetetracarboxylic acid, 4,4'-Hbpy = monoprotonated 4,4'-bipyridine, and hmt = hexamethylenetetramine). Complexes 2, 3, and 4 have rectangular pores with the size of 6.5 A x 4.5 A, 6 A x 7 A, and 10.1 A x 11.8 A, respectively, while 5 has a channel of 7.4 A x 9.6 A. The complexes show interesting magnetic properties due to the different coordination modes of the carboxylate groups and the presence of auxiliary ligands. On lowering the temperature, the magnetic interactions in 2 are changed from antiferromagnetic to ferromagnetic. For 3, the antiferromagnetic interactions weaken sharply at low temperature. Complex 4 shows ferromagnetic interactions while 5 is antiferromagnetic.     

Hydrothermal Synthesis and Crystal Structure of a Zinc(Ⅱ)Coordination Polymer Assembled by Dpphen and H_2btec/btec

<正>A new metal-organic coordination polymer[Zn_2(dpphen)_2(H_2btec)(btec)_(0.5)]_n (dpphen=4,7-diphenyl-1,10-phenanthroline,H_4btec=1,2,4,5-benzenetetracarboxylic acid)1 was obtained via hydrothermal synthesis and characterized by elemental analysis,TG,IR spectrum and single-crystal X-ray diffraction.The complex crystallizes in the monoclinic system,space group P2_l/n with a=16.2996(14),b=14.3332(12),c=25.247(2)(?),β=103.4050(10)°,V=5737.7(9)(?)~3, C_(63)H_(37)N_4O_(12)Zn_2,M_r=1172.71,D_c=1.358 g/cm~3,μ(MoKα)=0.902 mm~(-1),F(000)= 2396,Z=4, the final R=0.0684 and wR=0.1281 for 3728 observed reflections(I2σ(I)).It exhibits a two-dimensional network structure constructed by mixed ligands of dpphen and H_2btec/btec.     

Synthesis,Crystal Structure and Magnetic Properties of a Ni（Ⅱ） Supramolecular Complex Based on Aromatic Polycarboxylate Ligand

A Ni(Ⅱ) supramolecular complex,[Ni 2 (btec)(3py) 2 (H 2 O) 8 ](H 2 O) 4 (1),has been synthesized by Ni(ClO 4) 2 ·6H 2 O,benzene-1,2,4,5-tetracarboxylic acid (H 4 btec) and terminal ligand 3-hydroxypyridine (3py) in aqueous solution.The title compound crystallizes in triclinic system,space group P1,with a=8.5637(12),b=9.4138(13),c=10.3611(14),α=67.9540(10),β=85.1740(10),γ=76.9890(10)°,V=754.33(18) 3,Z=2,M r=386.96,D c=1.704 Mg/m 3,μ=1.345 mm-1,F(000)=402,the final R=0.0222 and wR=0.0563 for 2675 observed reflections with I > 2σ(Ⅰ).The adjacent discrete molecules are further self-assembled by intermolecular π-π and O-H···O hydrogen bonding interactions to construct a 3D supramolecular framework.Magnetic measurement shows weak ferromagnetic interaction in the range of 2～300 K.     

苯四甲酸桥连的镍配合物[Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O的合成及结构

At room temperature, a coordination polymer [Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O was synthesized by reaction of NiCl2·6H2O, 1,2,4,5-benzenetetracarboxylic dianhydridc and imidazole in a water/THF solution. The structure was determined by X-ray diffraction crystal structure analysis. It crystallizes in triclinic P1 space group with the crystal cell parameters of a=0.67542 (2) nm, b=1.000 14 (1) nm, c=1.09088 (3) nm, α=74.140(2)°, β= 74.388(1)°, y=73.239(2)°, and V=0.664 09(3) nm3, Z=1. The crystal structure shows that Ni1 atom is coordinated by four water and two imidazole molecules, while Ni2 is coordinated by four water molecules and two carboxyl oxygen atoms. The 1,2,4,5-benzenetetracarboxylate ions bridge Ni2 coordination centers to form one-dimensional chain structure. Moreover, the chains are further linked together by hydrogen bonds to form a two-dimensional network. CCDC: 295873.     

New two-dimensional metal-organic networks constructed from 1,2,4,5-benzenetetracarboxylate and chelate ligands

Two novel nickel coordination polymers [Ni(2)(2,2'-bipy)(2)(OH)(2)(H(2)btec)](3)(n)(1) and [Ni(2)(1,10'-phen)(2)(H(2)O)(2)(btec)](n)(2) (btec = 1,2,4,5-benzenetetracarboxylate) have been hydrothermally synthesized and characterized by elemental analyses, IR and XPS spectra, TG analysis, X-ray powder diffraction, and single crystal X-ray diffraction. Crystal data for 1: C(90)H(66)N(12)O(30)Ni(6), monoclinic P2(1)/c, a = 10.905(2) A, b = 18.006(4) A, c = 20.551(4) A, beta = 94.91(3) degrees, Z = 2. Crystal data for 2: C(34)H(22)N(4)O(10)Ni(2), monoclinic P2(1)/n, a = 10.122(2) A, b = 9.3106(19) A, c = 15.690(3) A, beta = 92.03(3) degrees, Z = 2. Compound 1 exhibits a novel one-dimensional chainlike structure, in which the dinuclear Ni centers are linked by the btec ligands. Furthermore, the adjacent chains are linked into a 2-D wavelike layer via the strong OH.O hydrogen bonding interactions. Compound 2 possesses an unusual two-dimensional steplike network with interesting rhombic grids. Both compounds exhibit unprecedented metal-organic ligand construction modes in [M/btec/L] (M = transition metal; L = chelate ligands) systems. The magnetic behaviors of compounds 1 and 2 have been studied.     

Synthesis, Crystal Structure and Characterization of a New Manganese(Ⅱ)Tetracarboxylate

By hydrothermal synthesis,a manganese(Ⅱ)tetracarboxylate [Mn(2,2'-bipyridi-ne)btec)o.5(H2O)]2n(H4btec=1,2,4,5-benzenetetracarboxylic acid)was obtained and characteri-zed by single-crystal X-ray diffraction,IR,elemental analysis and thermogravimetrie analysis.It crystallizes in triclinic,space group P(1),with a=7.721(4),b=8.905(5),c=10.712(6)(A),α=80.899(8),β=70.371(8),γ=78.201(8)°,z=2,V=675.8(7)(A)3,Mr=354.20,Dc=1.741 g/cm3,μ=1.007mm-1,F(000)=360,S=0.956,(△/σ)max=0.000,the final R=0.0490 and wR=0.1262.This compound presents an infinite 1D polymer featuring a double-chain structure.The Mn(Ⅱ)ion is five-coordinated.The four carboxylate groups of btec4- are all deprotonated and coordinated to four Mn atoms in a monodentate fashion,forming a 1D double chain structure with a cavity.Such chains are interconnected by π-π stacking interactions into 2D layers which are further interlinked into a supramolecular structure by hydrogen bonds.     

Five new manganese-mu-azido 2D compounds synthesized in aqueous hydrazoic acid from pyrazine derivatives

The syntheses, structural characterization, and magnetic behavior of five new 2D manganese(II) complexes with empirical formulas [Mn(N(3))(2)(2,6-DiMepyz)(H(2)O)](n)() (1), [Mn(N(3))(2)(Etpyz)(H(2)O)](n)() (2), [Mn(N(3))(2)(H(2)O)(2)](n)()(2,3-DiMepyz)(n)() (3), [Mn(N(3))(2)(Clpyz)(2)](n)() (4), and [Mn(N(3))(2)(Ipyz)(2)](n)() (5) (pyz = pyrazine (1,4-diazine)) are reported. 1 crystallizes in the monoclinic system, space group P2(1)/c, with unit cell parameters a = 7.513(4) A, b = 17.438(7) A, c = 8.404(4) A, beta = 94.53(4) degrees , and Z = 4. 2 crystallizes in the triclinic system, space group P, with unit cell parameters a = 7.386(2) A, b = 8.434(2) A, c = 9.442(3) A, alpha = 71.82(2) degrees , beta = 72.08(2) degrees , gamma = 88.54(2) degrees , and Z = 2. 3 crystallizes in the monoclinic system, space group C2/c, with unit cell parameters a = 20.438(7) A, b = 7.711(2) A, c = 7.457(2) A, beta = 93.76(3) degrees , and Z = 4. 4 crystallizes in the orthorhombic system, space group Pbca, with unit cell parameters a = 8.600(2) A, b = 13.440(4) A, c = 24.083(7) A, and Z = 8. 5 crystallizes in the orthorhombic system, space group Pbca, with unit cell parameters a = 8.521(2) A, b = 13.787(3) A, c = 26.237(5) A, and Z = 8. The compounds 1-5 have only azido bridging ligands. In 1-3 each manganese atom is linked to the four nearest neighbors by only end-to-end azido bridges, forming square layers. 4 and 5 show alternating end-to-end and end-on azido bridges between manganese atoms. The magnetic properties of 1-5 are reported. At high temperatures the plots of chi(M) or chi(M)T vs T for the 1-3 compounds can be fitted as homogeneous 2D systems with J = -4.9, -4.4, and -3.9 cm(-)(1) for 1-3, respectively. For 1, 3, and 5 magnetic ordering and spontaneous magnetizations is achieved below T(c) = 35, 29, and 22 K, respectively, whereas 2 and 4 do not show spontaneous magnetization up to 2 K.     

A Three-dimensional Supramolecular Complex {[Co(H2btec)(2,2'-bipy)(H2O)3]·H2O}n Assembled via Hydrogen Bonding and π-π Stacking Interactions

A new cobalt compound, {[Co(H2btec)(2,2'-bipy)(H2O)3]·H2O}n (1, H4btec =1,2,4,5-benzenetetracarboxylic acid, 2,2'-bipy = 2,2'-bipyridine), has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR and X-ray powder diffraction. The crystal belongs to the triclinic system, space group P-1, with a = 7.230(3), b = 11.626(5), c =14.001(6) (A), α = 108.12(0)°, β= 95.85(0)°, V= 1095.33(157)(A)3, C20H20CoN2O12, Mr= 539.31,Z=2, Dc = 1.635 g/cm3,μ = 0.855 mm-1, F(000) = 554, R = 0.0427 and wR = 0.1042 for 3883 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). The title compound features a discrete molecular structure, which is connected with each other through extensive O-H…O hydrogen bonds into an intricate 3D supramolecular network. Additionally, two different patterns of π-π stacking interactions further consolidate the framework.     

A new route for preparing coordination polymers from hydrothermal reactions involving in situ ligand synthesis

The coordination chemistry of inorganic cobalt salt and the organic ligands H(4)bbh (=benzene-1,2,4,5-bihydrazide) and H(3)bcbh (=benzene-4-carboxylate-1,2-bihydrazide) generated through the in situ hydrothermal acylate reaction of H(4)bta (=benzene-1,2,4,5-tetracarboxylic acid) and H(3)btc (=benzene-1,2,4-tricarboxylic acid) with hydrazine hydrate, respectively, has been investigated. Three new coordination polymers were prepared and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The compound [Co(micro(3)-H(2)bbh)(phen)](n)() (1) (triclinic space group P with a = 9.762(4) A, b = 10.169(4) A, c = 11.143(4) A, alpha = 80.96(3) degrees, beta = 64.49(3) degrees, gamma = 71.88(3) degrees, Z = 2) was synthesized from the reaction of CoCl(2).6H(2)O, H(4)bta (=benzene-1,2,4,5-tetracarboxylic acid), N(2)H(4).H(2)O, phen (=1,10-phenanthroline) and H(2)O, and consists of one-dimensional double-chains. [Co(micro(4)-H(2)bbh)(H(2)O)(2)](n)() (2) (monoclinic space group P2(1)/c with a = 6.8687(5) A, b = 7.5943(6) A, c = 10.0401(6) A, beta = 95.250(4) degrees, Z = 2) was generated by the combination of CoCl(2).6H(2)O, H(4)bta, N(2)H(4).H(2)O, and H(2)O. It adopts a three-dimensional structural motif in the solid state with channels consisting of 20-numbered rings. [Co(micro(3)-Hbcbh)(bpy)](n)() (3) (monoclinic space group Cc with a = 9.9464(13) A, b = 23.685(5) A, c = 7.9491 (16) A, beta = 117.677(13) degrees, Z = 4) was obtained from the mixture of CoCl(2).6H(2)O, N(2)H(4).H(2)O, H(3)btc (=benzene-1,2,4-tricarboxylic acid), bpy (=2,2'-dipyridyl), and H(2)O, and features a two-dimensional plane. The results of magnetic research indicate that there exist antiferromagnetic interactions between Co centers in both compounds 1 and 2.     

Sandwich-type germanotungstates: structure and magnetic properties of the dimeric polyoxoanions [M4(H2O)2(GeW9O34)2]12 - (M = Mn2+, Cu2+, Zn2+, Cd2+)

The novel dimeric germanotungstates [M(4)(H(2)O)(2)(GeW(9)O(34))(2)](12)(-) (M = Mn(2+), Cu(2+), Zn(2+), Cd(2+)) have been synthesized and characterized by IR spectroscopy, elemental analysis, magnetic measurements, and (183)W-NMR spectroscopy. X-ray single-crystal analyses were carried out on Na(12)[Mn(4)(H(2)O)(2)(GeW(9)O(34))(2)].38H(2)O (Na(12)()-1), which crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.0419(8) A, b = 17.8422(10) A, c = 21.1626(12) A, beta = 93.3120(10) degrees, and Z = 2; Na(11)Cs(2)[Cu(4)(H(2)O)(2)(GeW(9)O(34))(2)]Cl.31H(2)O (Na(11)()Cs-2) crystallizes in the triclinic system, space group P, with a = 12.2338(17) A, b = 12.3833(17) A, c = 15.449(2) A, alpha = 100.041(2) degrees, beta = 97.034(2) degrees, gamma = 101.153(2) degrees, and Z = 1; Na(12)[Zn(4)(H(2)O)(2)(GeW(9)O(34))(2)].32H(2)O (Na(12)()-3) crystallizes in the triclinic system, space group P, with a = 11.589(3) A, b = 12.811(3) A, c = 17.221(4) A, alpha = 97.828(6) degrees, beta = 106.169(6) degrees, gamma = 112.113(5) degrees, and Z = 1; Na(12)[Cd(4)(H(2)O)(2)(GeW(9)O(34))(2)].32.2H(2)O (Na(12)()-4) crystallizes also in the triclinic system, space group P, with a = 11.6923(17) A, b = 12.8464(18) A, c = 17.616(2) A, alpha = 98.149(3) degrees, beta = 105.677(3) degrees, gamma = 112.233(2) degrees, and Z = 1. The polyanions consist of two lacunary B-alpha-[GeW(9)O(34)](10)(-) Keggin moieties linked via a rhomblike M(4)O(16) (M = Mn, Cu, Zn, Cd) group leading to a sandwich-type structure. (183)W-NMR studies of the diamagnetic Zn and Cd derivatives indicate that the solid-state polyoxoanion structures are preserved in solution. EPR measurements on Na(12)()-1 at frequencies up to 188 GHz and temperatures down to 4 K yield a single, exchange-narrowed peak, at g(iso) = 1.9949, typical of Mn systems, and an upper limit of |D| = 20.0 mT; its magnetization studies still await further theoretical treatment. Detailed EPR studies on Na(11)()Cs-2 over temperatures down to 2 K and variable frequencies yield g( parallel ) = 2.4303 and g( perpendicular ) = 2.0567 and A( parallel ) = 4.4 mT (delocalized over the Cu(4) framework), with |D| = 12.1 mT. Magnetization studies in addition yield the exchange parameters J(1) = -11 and J(2) = -82 cm(-)(1), in agreement with the EPR studies.     

Synthesis,structure, and magnetic properties of two new vanadocarboxylates with three-dimensional hybrid frameworks

(V(III)(OH))(2)[C(6)H(2)(CO(2))(4)].4H(2)O (labeled MIL-60) and V(III)(OH)[(2)(O(2)C)C(6)H(2)(COOH)(2)].H(2)O (labeled MIL-61) were hydrothermally synthesized from mixtures of VCl(3), 1,2,4,5-benzenetetracarboxylic acid, and water heated for 3 days at 473 K. The structure of MIL-60 was solved from single-crystal X-ray diffraction data in the triclinic centrosymmetric P1 (No. 2) space group with lattice parameters a = 6.3758(5) A, b = 6.8840(5) A, c = 9.0254(5) A, alpha = 69.010(2) degrees, beta = 85.197(2) degrees, gamma = 79.452(2) degrees, V = 363.53(5) A(3), and Z = 1. The structure of MIL-61 was ab initio determined from an X-ray powder diffraction pattern. MIL-61 crystallizes in the Pnma (No. 62) orthorhombic space group with lattice parameters a = 14.8860(1) A, b = 6.9164(1) A, c = 10.6669(2) A, V = 1098.23(3) A(3), and Z = 4. Both structures contain the same inorganic building block that consists of trans chains of V(III)O(4)(OH)(2) octahedra. The three-dimensional frameworks of MIL-60 and MIL-61 are constituted by the linkage of these chains via the organic molecules so delimiting the channels or cages where the water molecules are encapsulated. The magnetic behavior of these two phases is presented: MIL-60 is paramagnetic, and MIL-61 antiferromagnetically orders below T(N) = 55(5) K.     

Puckered-boat conformation hexameric water clusters stabilized in a 2D metal-organic framework structure built from CuII and 1,2,4,5-benzenetetracarboxylic acid

1,2,4,5-Benzenetetracarboxylic acid (btcH(4)) reacts with Cu(NO(3))(2).6H(2)O to form 2D coordination polymeric structure [[Cu(2)(btc)(Py)(4).2H(2)O].4H(2)O](n), 1, in the presence of pyridine from water at room temperature. Puckered-boat-shaped hexameric water clusters resulting from four free water molecules and two water molecules coordinating to metal ions join these sheets to make a 3D network. These water clusters behave as pillars to join those sheets which is the key factor stabilizing the 3D network. Thermal analysis, X-ray powder diffraction, and X-ray structure analysis have been used to characterize this compound. Crystal data for 1 follow: triclinic space group P1, a = 8.905(3) A, b = 11.137(4) A, c = 17.484(2) A, alpha = 82.342(6) degrees, beta = 81.312(3) degrees, gamma = 82.361(4) degrees V= 1687.5(1)A(3), Z = 2, R1 = 0.0331, wR2 = 0.0886, S =1.066.     

Preparation of acentric porous coordination frameworks from an interpenetrated diamondoid array through anion-exchange procedures: crystal structures and properties

The formation, crystal structures, and properties of a series of three-dimensional (3-D) Cu(II) coordination polymers, [[Cu(L)2(H2O)2](PF6)2(H2O)(1.25)]n (1), [[CuL(N3)2](H2O)(1.5)]n (2), and [[CuL(H2O)(SO4)](H2O)2]n (3), with an angular bridging ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L) are reported. Complex 1 crystallizes in the tetragonal I4(1)/a space group (a = b = 13.462(2) A, c = 46.47(1) A, Z = 8), complex 2 in the orthorhombic Pna2(1) space group (a = 6.379(2) A, b = 10.060(3) A, c = 27.232(9) A, Z = 4), and complex 3 in the orthorhombic P2(1)2(1)2(1) space group (a = 5.510(2) A, b = 10.576(4) A, c = 28.34(1) A, Z = 4). Different polymeric frameworks are obtained by only varying the counterions. These include the 2-fold interpenetrated diamondoid structure of 1, the acentric alpha-Po network of 2, and the chiral open framework of 3 with (6(3)).(6(9).8) topology. The interesting anion-exchange, porous, and magnetic properties of these coordination supramolecules have been investigated in detail.     

Synthesis and Crystal Structure of a Novel Heterometallic Complex with 1,2,4,5-Benzenetetracarboxylic Acid and 1,3,5-Tris（imidazol-1-ylmethyl）-2,4,6-trimethylbenzene

A novel heterometallic complex,[Zn4Ni(OH)2(btec)2(titb)2(H2O)2]·2H2O(1)(H4btec=1,2,4,5-benzenetetracarboxylic acid,titb=1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trime-thylbenzene),has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.817(10),b=11.878(11),c=14.569(14),α=71.762(12),β=76.122(13),γ=71.493(13)°,V=1665(3)3,C62H62N12O22Zn4Ni,Mr=1647.43,Dc=1.643 g/cm3,F(000)=842,μ=1.784 mm-1 and Z=1.The final R=0.0531 and wR=0.0890 for 3545 observed reflections(Ⅰ 2σ(Ⅰ)).In the title complex,the btec ligand acts as a five-dentate bridging ligand to link up zinc and nickel atoms into a lamellar framework,which are further interlinked into a 3-D framework via the titb ligands.     

Synthesis and structural characterization of a new series of vanadoselenites, [Se(x)V(4-x)O(12-x)](4-x)- (x=1,2)

Two new vanadoselenites, [SeV(3)O(11)](3)(-) and [Se(2)V(2)O(10)](2)(-), were synthesized by reacting SeO(2) with VO(3)(-). Single-crystal X-ray structural analyses of [(n-C(4)H(9))(4)N](3)[SeV(3)O(11)].0.5H(2)O [orthorhombic, space group P2(1)2(1)2, a = 22.328(5) A, b = 44.099(9) A, c = 12.287(3) A, Z = 8] and [[(C(6)H(5))(3)P](2)N](2)[Se(2)V(2)O(10)] [monoclinic, space group P2(1)/n, a = 12.2931(3) A, b = 13.5101(3) A, c = 20.9793(5) A, beta = 106.307(1) degrees, Z = 2] revealed that both anions are composed of Se(x)()V(4)(-)(x)()O(4) rings. The (51)V, (77)Se, and (17)O NMR spectra established that both [SeV(3)O(11)](3)(-) and [Se(2)V(2)O(10)](2)(-) anions maintain this ring structure in solution.     

New Cd(II)-, Co(II)-, and Cu(II)-containing coordination polymers synthesized by using the rigid ligand 1,2-bis(3-pyridyl)ethyne (3,3'-DPA)

Four new organic/inorganic coordination polymers, [Cd(C(10)H(8)N(2))(2)(H(2)O)(2)(NO(3))(2)](n)(1), [Co(C(10)H(8)N(2))(H(2)O)NO(3)CH(3)OH](n)(2), [Cu(C(10)H(8)N(2))(CH(3)OH)(NO(3))(2)](n) (3), and [Cu(C(10)H(8)N(2))(hfac)(2)](n)(4), were synthesized by using the rigid ligand 1,2-bis(3-pyridyl)ethyne (3,3'-DPA). Complex 1 crystallizes in space group P2/n: a = 12.462(2) A, b = 9.485(1) A, c = 13.383(2) A, beta = 96.629(2) degrees, V = 1559.6(3) A(3), Z = 4. Complex 2 crystallizes in space group Fddd: a = 9.248(4) A, b = 19.982(7) A, c = 35.093(16) A, V = 6485.0(4) A(3), Z = 8. Complex 3 crystallizes in space group I2/a: a = 18.315(2) A, b = 8.517(1) A, c = 20.494(3) A, beta = 104.042(2) degrees, V = 3101.2(7) A(3), Z = 8. Complex 4 crystallizes in space group P21/c: a = 6.576(1) A, b = 16.189(1) A, c = 11.653(1) A, beta = 91.337(1) degrees, V = 1240.3(2) A(3), Z = 2. The coordination polymers display a variety of structural architectures, ranging from sinusoidal and zigzag chains (1, 3, 4) to two-dimensional channel-type architectures (2). The effects of the orientation of the nitrogen atom in the pyridine rings on the resultant structures are discussed.     

Hydrothermal synthesis,structures, and magnetic properties of three novel 5-aminoisophthalic acid ligand bridged transition metal cation polymers

Three novel 5-aminoisophthalic acid (AIP) bridged polymers [Co(C(8)NH(5)O(4))(H(2)O)](n)() (1), [Ni(C(8)NH(5)O(4))(H(2)O)(2)](n)() (2), and [Zn(C(8)NH(5)O(4))(H(2)O)](n)() (3) were synthesized by hydrothermal reactions and characterized by IR, Raman, elemental analysis, ESR, and magnetic measurements. X-ray single-crystal analyses were carried out for [Co(C(8)NH(5)O(4))(H(2)O)](n)() (1), which crystallizes in the triclinic system, space group P1 macro, with a = 6.477(1) A, b = 7.130(1) A, c = 9.826(2) A, alpha = 108.9(1) degrees, beta = 93.97(3) degrees, gamma = 98.82(3) degrees, and Z = 2; for [Ni(C(8)NH(5)O(4))(H(2)O)(2)](n)() (2), in the triclinic system, space group P1 macro, a = 6.425(1) A, b = 8.115(2) A, c = 10.146(2) A, alpha = 113.09(3)(o), beta = 99.64(3)(o), gamma = 98.90(3)(o), and Z = 2; and for [Zn(C(8)NH(5)O(4))(H(2)O)](n)() (3), in the monoclinic system, space group P2(1)/n, a = 9.044(1) A, b = 8.264(1) A, c = 11.646(1) A, beta = 100.77(1) degrees, and Z = 4. The single X-ray diffraction studies reveal that 1 consists of an infinite honeycomb layer formed by four crystallographically independent motifs packed alternatively together; 2 consists of an infinite neutral railroad-like linear polymer, and 3 consists of infinite layers of alternating four-coordinated Zn(II) cations and AIP ligands. Finally, they are all packed into beautiful three-dimensional frameworks through complicated hydrogen bonding. Antiferromagnetic and ferromagnetic behaviors were observed for 1 and 2 from the magnetic measurements.     

Structure,magnetism, and electrochemistry of the multinickel polyoxoanions [Ni6As3W24O94(H2O)2]17-, [Ni3Na(H2O)2(AsW9O34)2]11-, and [Ni4Mn2P3W24O94(H2O)2]17-

The three novel, multi-nickel-substituted heteropolytungstates [Ni(6)As(3)W(24)O(94)(H(2)O)(2)](17)(-) (1), [Ni(3)Na(H(2)O)(2)(AsW(9)O(34))(2)](11)(-) (2), and [Ni(4)Mn(2)P(3)W(24)O(94)(H(2)O)(2)](17)(-) (3) have been synthesized and characterized by IR, elemental analysis, electrochemistry, and magnetic studies. Single-crystal X-ray analysis was carried out on Na(16.5)Ni(0.25)[Ni(6)As(3)W(24)O(94)(H(2)O)(2)].54H(2)O, which crystallizes in the triclinic system, space group P1, with a = 17.450(4) A, b = 17.476(4) A, c = 22.232(4) A, alpha = 85.73(3) degrees, beta = 89.74(3) degrees, gamma = 84.33(3) degrees, and Z = 2, Na(11)[Ni(3)Na(H(2)O)(2)(AsW(9)O(34))(2)].30.5H(2)O, which crystallizes in the triclinic system, space group P1, with a = 12.228(2) A, b = 16.743(3) A, c = 23.342(5) A, alpha = 78.50(3) degrees, beta = 80.69(3) degrees, gamma = 78.66(3) degrees, and Z = 2, and Na(17)[Ni(4)Mn(2)P(3)W(24)O(94)(H(2)O)(2)].50.5H(2)O, which crystallizes in the monoclinic system, space group P2(1)/c, with a = 17.540(4) A, b = 22.303(5) A, c = 35.067(7) A, beta = 95.87(3) A, and Z = 4. Polyanion 1 consists of two B-alpha-(Ni(3)AsW(9)O(40)) Keggin moieties linked via a unique AsW(6)O(16) fragment, leading to a banana-shaped structure with C(2)(v)() symmetry. The mixed-metal tungstophosphate 3 is isostructural with 1. Polyanion 2 consists of two lacunary B-alpha-[AsW(9)O(34)](9)(-) Keggin moieties linked via three nickel(II) centers and a sodium ion. Electrochemical studies show that 1-3 exhibit a unique and reproducible voltammetric pattern and that all three compounds are stable in a large pH range. An investigation of the magnetic properties of 1-3 indicates that the exchange interactions within the trimetal clusters are ferromagnetic. However, for 1 and 3 intra- and intermolecular interactions between different trinuclear clusters are also present.     

A Three-dimensional Neodymium(III)-potassium(I) Coordination Polymer

The title compound [NdK(btec)(H2O)2]n 1 was synthesized via the hydrothermal reaction of Zn(OAc)2·H2O, Nd(NO3)3 and KOH with 1,2,4,5-benzenetetra-carboxylic acid (H4btec), and characterized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in monoclinic, space group P21/c with a = 8.9023(3), b = 7.8954(1), c = 17.6249(5)A, β = 91.857(1)o, V = 1238.16(6) -3, Z = 4, C10H6KNdO10, Mr = 469.49, Dc = 2.519 g/cm3, F(000) = 900 and μ(MoKα) = 4.585 mm-1.The final R = 0.0404 and wR = 0.0832 for 2197 observed reflections with I > 2σ(I) and R = 0.0431 and wR = 0.0854 for all data.X-ray diffraction reveals that the btec ligand serves as a (16-bridging ligand to link the Nd(III) and K(I) atoms into a three-dimensional coordination polymer.Photoluminescent investigation shows that the title compound displays strong emission in the blue region, which may be attributed to an intraligand emission state.