Five new zinc phosphite structures: tertiary building blocks in the construction of hybrid materials

The syntheses and structures of five new zinc phosphites [Zn(HPO(3))(C(4)H(6)N(2))] (1), [Zn(2)(HPO(3))(2)(C(10)H(10)N(2))(2)](2) (2), [Zn(HPO(3))(C(14)H(14)N(4))(0.5)] (3), [Zn(2)(HPO(3))(2)(C(14)H(14)N(4))].0.4H(2)O (4), and [Zn(2)(HPO(3))(2)(C(14)H(14)N(4))] (5) are reported. In compounds 1-3, the zinc atoms are ligated by 1-methylimidazole, 1-benzylimidazole, and 1,4-bis(imidazol-1-ylmethyl)benzene, respectively, while compounds 4 and 5 are synthesized in the presence of the same bifunctional ligand, 1,3-bis(imidazol-1-ylmethyl)benzene. The inorganic framework of compound 1 is composed of vertex-shared ZnO(3)N and HPO(3) tetrahedra that form 4-rings, which, in turn, are linked to generate a one-dimensional ladder structure. In 2, the inorganic framework is composed of 4-rings and 8-rings to form the well-known 4.8(2) 2D network. This is connected via C-H...pi interactions between 1-benzylimidazole ligand to generate a pseudo-pillared-layer structure. In 3, the inorganic framework again has the 4.8(2) topology pillared by the bis(imidazole) ligand, 1,3-bis(imidazol-1-ylmethyl)benzene. In 4, a new layer pattern is observed. Specifically, three edge-sharing 4-rings form triple-fused 4-rings. These tertiary building units are further connected to form 12-rings. The alternating triple 4-rings and 12-rings form a previously unknown 2D inorganic sheet. The sheets are joined together by the bis(imidazole) ligand, 1,3-bis(imidazol-1-ylmethyl)benzene, to generate a 3D pillared-layer structure. In 4, benzene rings and imidazole rings stack in a zigzag pattern in the interlayer space. A significant role for the triple 4-ring tertiary building unit in the formation of hybrid inorganic/organic metal phosphite structures is proposed for 4 and 5. In 5, the triple 4-rings fuse to give a 1D stair-step structure. Calculations show that the triple 4-ring pattern observed in the linear ladder structure of 1 is more stable than that in the stair step pattern of 5.     

Novel zinc phosphate topologies defined by organic ligands

Six new zinc phosphates [C18H20N4][Zn4(HPO4)4(H2PO4)2(C18H18N4)3].2H2O (1), [Zn4(HPO4)4(C18H18N4)3].4H2O (2), [Zn3(HPO4)3(H2PO4)(C22H22N8)0.5(C22H24N8)0.5] (3), [Zn2(HPO4)2(C18H16N4)] (4), [Zn(HPO4)(C18H14N2)] (5), and [Zn2(HPO4)2(C12H10N4)] (6) have been synthesized under mild hydrothermal conditions in the presence of 1,4-bis(N-benzimidazolyl)butane (L1), 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (L2), 1,4-bis(imidazol-1-ylmethyl)naphthalene (L3), 9-(imidazol-1-ylmethyl)anthracene (L4), and 1,4-bis(1-imidazolyl)benzene (L5), respectively, and their structures were determined by X-ray crystallography. Compound 1 exhibits a unique inorganic motif of isolated 8-rings interconnected by L1. Compound 2, also formed from L1, contains a previously unobserved chain structure composed of edge-sharing 4-rings and 8-rings. Compound 3, prepared from L2, possesses an unusual one-dimensional framework, which is composed of vertex-sharing 4-rings and triple fused 4-rings. The inorganic portions of 4, 5, and 6 each adopt a layer structure. The sheets in 4 and 5 have a 4.8(2) topology, and in 6, a 6(3) topology is observed. The zinc atoms in compounds 1-6 are all tetrahedrally coordinated by a combination of phosphate groups and organic ligands. Potential relationships between the inorganic motifs reported in the present study are identified. These are indicative of a possible pattern of self-assembly of zinc and phosphorus tetrahedra and indicative of the role of the organic ligands in the formation of hybrid structures.     

Syntheses, structures, and magnetic properties of inorganic-organic hybrid cobalt(II) phosphites containing bifunctional ligands

Seven new cobalt(II) phosphites, [Co(HPO(3))(C(14)H(14)N(4))(H(2)O)(2)].2H(2)O (1), [Co(HPO(3))(C(22)H(18)N(4))].H(2)O (2), [Co(2)(HPO(3))(2)(C(22)H(18)N(4))(2)H(2)O].H(2)O (3), [Co(2)(HPO(3))(2)(C(12)H(10)N(4))(1.5)H(2)O].1.5H(2)O (4), [Co(HPO(3))(C(14)H(14)N(4))(0.5)].H(2)O (5), [Co(HPO(3))(C(18)H(16)N(4))(0.5)] (6), and [Co(HPO(3))(C(18)H(16)N(4))(0.5)] (7) were synthesized in the presence of 1,2-bis(imidazol-1-ylmethyl)benzene (L1), 1,4-bis(benzimidazol-1-ylmethyl)benzene (L2), 1,3-bis(benzimidazol-1-ylmethyl)benzene (L3), 1,4-bis(1-imidazolyl)benzene (L4), 1,4-bis(imidazol-1-ylmethyl)benzene (L5), 1,4-bis(imidazol-1-ylmethyl)naphthalene (L6), and 1,5-bis(imidazol-1-ylmethyl)naphthalene (L7), respectively, and their structures were determined by X-ray crystallography. Compound 1 is a molecular compound in which two cobalt(II) ions are held together by double mu-O linkages. The inorganic framework of compounds 2 and 3 are composed of vertex-shared CoO(2)N(2)/CoO(3)N(2) and HPO(3) polyhedra that form four rings; these are further linked by an organic ligand to generate 2D sheets. Compounds 4 and 5 both have 1D inorganic structures, with the bifunctional ligands connected to each side of the ladder by coordination bonds to give 2D hybrid sheets. A 3D organically pillared hybrid framework is observed in 6 and 7. In 6, the stacking of the interlayer pillars gives rise to a small hydrophobic channel that extends through the entire structure parallel to the sheets. The temperature-dependent magnetic susceptibility measurements of these compounds show weak interactions between the metal centers, mediated through the mu-O and/or O-P-O linkages.     

Syntheses and characterization of six coordination polymers of zinc(II) and cobalt(II) with 1,3,5-benzenetricarboxylate anion and bis(imidazole) ligands

Six new coordination polymers, namely [Zn1.5(BTC)(L1)(H2O)2].1.5H2O (1), [Zn3(BTC)2(L2)3] (2), [Zn3(BTC)2(L3)1.5(H2O)].H2O (3), [Co6(BTC)4(L1)6(H2O)3].9H2O (4), [Co1.5(BTC)(L2)1.5].0.25H2O (5), and [Co4(BTC)2(L3)2(OH)2(H2O)].4.5H2O (6), where L1 = 1,2-bis(imidazol-1-ylmethyl)benzene, L2 = 1,3-bis(imidazol-1-ylmethyl)benzene, L3 = 1,1'-(1,4-butanediyl)bis(imidazole), and BTC = 1,3,5-benzenetricarboxylate anion, were synthesized under hydrothermal conditions. In 1-6, each of L1-L3 serves as a bidentate bridging ligand. In 1, BTC anions act as tridentate ligands, and compound 1 shows a 2D polymeric structure which consists of 2-fold interpenetrating (6, 3) networks. In compound 2, BTC anions coordinate to zinc cations as tridentate ligands to form a net with (64.82)2(86)(62.8)2 topology. In compound 3, BTC anions act as tetradentate ligands and coordinate to zinc cations to form a net with (4.62.83)2(8.102)(4.6.83.10)2 topology. In compound 5, each BTC anion coordinates to three Co cations, and the framework of 5 can be simplified as (64.82)2(62.82.102)(63)2 topology. For 4 and 6, the 2D cobalt-BTC layers are linked by bis(imidazole) ligands to form 3D frameworks. In 6, the Co centers are connected by micro3-OH and carboxylate O atoms to form two kinds of cobalt-oxygen clusters. Thermogravimetric analyses (TGA) for these compounds are discussed. The luminescent properties for 1-3 and magnetic properties for 4-6 are also discussed in detail.     

Design and construction of coordination polymers based on 2,2'-dinitro-4,4'-biphenyldicarboxylate and semi-rigid N-donor ligands: diverse structures and magnetic properties

Eight 2D and 3D coordination polymers, [Mn(NBPDC)(1,4-bimb)](n) (1), [Zn(NBPDC)(1,4-bimb)](n) (2), [Cd(NBPDC)(1,4-bimb)](n) (3), [Mn(2)(NBPDC)(2)(1,3-bimb)(H(2)O)](n) (4), {Zn(NBPDC)(1,3-bimb)}(n) (5), [Cd(2)(NBPDC)(2)(1,3-bimb)(2)(H(2)O)](n) (6), [Mn(NBPDC)(4,4'-bimbp)](n) (7), and [Cd(2)(NBPDC)(2)(4,4'-bimbp)(2)](n) (8), (NBPDC = 2,2'-dinitro-4,4'-biphenyldicarboxyl acid, 1,4-bimb = 1,4-bis(imidazol-1-ylmethyl) benzene, 1,3-bimb = 1,3-bis(imidazol-1-ylmethyl) benzene, and 4,4'-bimbp = 4,4'-(bis(imidazol-l-ylmethylene)) biphenyl), have been prepared and structurally characterized. In these coordination polymers, NBPDC and three N-donor ligands link different metal ions and SBUs to construct diverse architectures. Compounds 1 and 3 are isomorphic, showing a two-fold interpenetrating pcu topology. Compound 2 presents a 2D (4, 4) net. Compound 4 is a hex framework built by the linkage of ligands with infinite rod-shaped SBUs. Compound 5 presents a unprecedented eight-fold interpenetrating sra topology. Compound 6 exhibits a unique 2D {6(3)}{6(5).8} topology with four-fold interpenetrating structure. Compound 7 presents a 3D hex topology, and compound 8 shows a (4, 4) net. The magnetic properties of compounds 1, 4, and 7 have been characterized. Compound 1 displays interesting spin-canting antiferromagnetism and metamagnetism simultaneously. Compound 7 exhibits spin-canting antiferromagnetism.     

Formation of one-, two-, and three-dimensional open-framework zinc phosphates in the presence of a tetramine

Five new open-framework zinc phosphates, encompassing the entire hierarchy of open-framework structures, have been synthesized hydrothermally in the presence of triethylenetetramine. The structures include one-dimensional ladders, two-dimensional layers, and three-dimensional structures as well as a zinc phosphate where the amine acts as a ligand. [C6N4H22]0.5[Zn(HPO4)2] (I): monoclinic, space group P2(1)/c (no. 14), a = 5.2677(1) A, b = 13.3025(1) A, c = 14.7833(1) A, beta = 96.049 degrees, Z = 4. [C6N4H22]0.5[Zn2(HPO4)3] (II): triclinic, space group P1 (no. 2), a = 7.515(1) A, b = 8.2553(1) A, c = 12.911(1) A, alpha = 98.654(1) degrees, beta = 101.274(1) degrees, gamma = 115.791(1) degrees, Z = 2. [C6N4H22]0.5[Zn2P2O8] (III): triclinic, space group P1 (no. 2), a = 8.064(1) A, b = 8.457(1) A, c = 9.023(1) A, alpha = 111.9(1) degrees, beta = 108.0(1) degrees, gamma = 103.6(1) degrees, Z = 2. [C6N4H22]0.5[Zn3(PO4)2(HPO4)] (IV): triclinic, space group P1 (no. 2), a = 5.218(1) A, b = 8.780(1) A, c = 16.081(1) A, alpha = 89.3(1) degrees, beta = 83.5(1) degrees, gamma = 74.3(1) degrees, Z = 2. [C6N4H20]0.5[Zn4P4O16] (V): monoclinic, space group P2(1)/c (no. 14), a = 9.219(1) A, b = 15.239(1) A, c = 10.227(1) A, beta = 105.2(1), Z = 4. The structure of I is composed of ZnO4 and HPO4 tetrahedra, which are edge-shared to form four-membered rings, which, in turn, form a one-dimensional chain (ladder). In II, these ladders are fused into a layer. The structures of III and IV comprise networks of ZnO4 and PO4 tetrahedra forming three-dimensional architectures. In V, the amine molecule coordinates to the Zn and acts as a pillar supporting the zinc phosphate layers, which possess infinite Zn-O-Zn linkages. The 16-membered one-dimensional channel in IV and the ZnO3N pillar, along with infinite Zn-O-Zn linkages in V, are novel features. The structure of the open-framework zinc phosphates is found to depend sensitively on the relative concentrations of the amine and phosphoric acid, with high concentrations of the latter favoring structures with lower dimensions.     

Synthesis, structure, and polymorphism studies in amine-templated open-framework zinc phosphites

Five new zinc phosphites, [C10N4H26][Zn2(HPO3)4].2H2O, 1, [C10N4H26][Zn5(H2O)4(HPO3)6].4H2O, 2, [C10N4H26][Zn4(HPO3)6].2H2O, 3, [C10N4H26][Zn4(HPO3)6].2H2O, 4, and [Zn2(HPO3)2(C10N4H24)], 5, were synthesized employing solvo/hydrothermal reactions in the presence of 1,4-bis (3-aminopropyl) piperazine (APPIP). Single crystal X-ray diffraction studies indicate that all the compounds form a hierarchy of structures. While the structures 1 and 2 are low-dimensional, 3-5 have three-dimensional connectivity. ZnO4 and HPO3 units form a 4-membered ring and are connected through their corners forming a one-dimensional chain structure in 1. 2 has one-dimensional ladders connected by ZnO2(H2O)4 octahedral units forming a layer with 4- and 8-membered apertures. Compounds 3 and 4 have similar molecular formulae and connectivity, which makes them polymorphic in nature. The amine molecules exist in gauche and all-trans form in 3 and 4, respectively. The amine molecule binds with the zinc center in 5 and acts as a pillar between the two zinc phosphite layers. The present study outlines the possible role of synthesis parameters for the isolation of a number of different structures by employing a single amine molecule, APPIP. The observation of polymorphic structures along with the interconvertibilities of one of the phases is important and noteworthy. The 31P chemical shifts observed in NMR studies, consistent with the single crystal data, have been correlated with the valence sum values of the oxygen that are bound with the distinct phosphorus.     

三种新型铜配合物的合成、结构及理论计算

合成了一个柔性配体1,3-二(N-咪唑基甲基)苯(mbix)(1), 并将其与不同Cu盐组装, 得到3个新配合物[Cu(mbix)2(H2O)]·2NO3·CH3OH(2), [Cu(mbix)(N3)(OAc)]·CH3OH(3)和[Cu(mbix)2]·SiF6·2CH3OH(4), 并对其进行了元素分析、红外光谱及X 射线单晶结构分析表征. 配合物2拥有二维二重贯穿结构, 配合物3中两个铜离子通过两个叠氮酸根桥连成双核铜, 它再通过配体连接形成一维绞链状结构, 而配合物4通过配体桥联成一维无限链状结构. 结果显示, 平衡阴离子在配合物的组装过程中起着非常重要的作用. 此外还对配体及3个配合物中配体的构象进行了理论计算.     

The role of Zn-OR and Zn-OH nucleophiles and the influence of para-substituents in the reactions of binuclear phosphatase mimetics

Analogues of the ligand 2,2'-(2-hydroxy-5-methyl-1,3-phenylene)bis(methylene)bis((pyridin-2-ylmethyl)azanediyl)diethanol (CH(3)H(3)L1) are described. Complexation of these analogues, 2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol (CH(3)HL2), 4-bromo-2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)phenol (BrHL2), 2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-nitrophenol (NO(2)HL2) and 4-methyl-2,6-bis(((2-phenoxyethyl)(pyridin-2-ylmethyl)amino)methyl)phenol (CH(3)HL3) with zinc(II) acetate afforded [Zn(2)(CH(3)L2)(CH(3)COO)(2)](PF(6)), [Zn(2)(NO(2)L2)(CH(3)COO)(2)](PF(6)), [Zn(2)(BrL2)(CH(3)COO)(2)](PF(6)) and [Zn(2)(CH(3)L3)(CH(3)COO)(2)](PF(6)), in addition to [Zn(4)(CH(3)L2)(2)(NO(2)C(6)H(5)OPO(3))(2)(H(2)O)(2)](PF(6))(2) and [Zn(4)(BrL2)(2)(PO(3)F)(2)(H(2)O)(2)](PF(6))(2). The complexes were characterized using (1)H and (13)C NMR spectroscopy, mass spectrometry, microanalysis, and X-ray crystallography. The complexes contain either a coordinated methyl- (L2 ligands) or phenyl- (L3 ligand) ether, replacing the potentially nucleophilic coordinated alcohol in the previously reported complex [Zn(2)(CH(3)HL1)(CH(3)COO)(H(2)O)](PF(6)). Functional studies of the zinc complexes with the substrate bis(2,4-dinitrophenyl) phosphate (BDNPP) showed them to be competent catalysts with, for example, [Zn(2)(CH(3)L2)](+), k(cat) = 5.70 ± 0.04 × 10(-3) s(-1) (K(m) = 20.8 ± 5.0 mM) and [Zn(2)(CH(3)L3)](+), k(cat) = 3.60 ± 0.04 × 10(-3) s(-1) (K(m) = 18.9 ± 3.5 mM). Catalytically relevant pK(a)s of 6.7 and 7.7 were observed for the zinc(II) complexes of CH(3)L2(-) and CH(3)L3(-), respectively. Electron donating para-substituents enhance the rate of hydrolysis of BDNPP such that k(cat)p-CH(3) > p-Br > p-NO(2). Use of a solvent mixture containing H(2)O(18)/H(2)O(16) in the reaction with BDNPP showed that for [Zn(2)(CH(3)L2)(CH(3)COO)(2)](PF(6)) and [Zn(2)(NO(2)L2)(CH(3)COO)(2)](PF(6)), as well as [Zn(2)(CH(3)HL1)(CH(3)COO)(H(2)O)](PF(6)), the (18)O label was incorporated in the product of the hydrolysis suggesting that the nucleophile involved in the hydrolysis reaction was a Zn-OH moiety. The results are discussed with respect to the potential nucleophilic species (coordinated deprotonated alcohol versus coordinated hydroxide).     

New amine-templated zinc phosphates with a temperature-induced increase of structural dimensionality

Three new amine-templated zinc phosphates, [C4N2H14][Zn(HPO4)2].H2O, AU-I, [C4N2H14][Zn2(H(0.5)PO4)2(H2PO4)], AU-II, and [C4N2H14][Zn5(H2O)(PO4)4], AU-III, are prepared by hydrothermal synthesis using an organic amine, N,N'-dimethylethylendiamine CH3NHCH2CH2NHCH3, as structure-directing agent. The three materials are prepared from the same reaction mixture, 1Zn(CH3CO2)2:3.05H3PO4:2.25CH3NHCH2CH2NHCH3:138H2O (pH = 5.1), AU-I at RT, AU-II at 60 degrees C, and AU-III at 170 degrees C. The materials are built from corner-sharing ZnO4 and PO4 tetrahedra forming chains, layers, or framework structures for AU-I to III, respectively, and are linked together by hydrogen bonds via the diprotonated amine ions. The complete hydrogen-bond scheme is resolved for these new compounds and reveals some interesting phenomena, for example, a hydrogen shared between two phosphate groups in AU-II, thereby forming H(0.5)PO4 groups. Furthermore, the water molecules are different; that is, in AU-I they act as hydrogen-bond donor and acceptor, whereas they act as ligand in AU-III with coordination to Zn. The structures of the compounds are determined by single-crystal X-ray diffraction analysis. AU-I, [C4N2H14][Zn(HPO4)2].H2O, crystallizes in the triclinic space group P-1, a = 8.215(2), b = 8.810(3), c = 8.861(3) A, alpha = 88.001(4) degrees , beta = 89.818(5) degrees , and gamma = 89.773(5) degrees , Z = 2. AU-II, [C4N2H14][Zn2(H(0.5)PO4)2(H2PO4)], is monoclinic, P2/n, a = 11.7877(4), b = 5.2093(2), c = 12.2031(4) A, beta = 98.198(1) degrees , Z = 2. AU-III, [C4N2H14][Zn5(H2O)(PO4)4], crystallizes in the orthorhombic space group Pna2(1) with lattice parameters, a = 20.723(2), b = 5.2095(6), c = 17.874(2) A, Z = 4. The phase stability investigated by systematic hydrothermal synthesis is presented, and the materials are further characterized by 31P solid-state MAS NMR, for example, by determination of 31P chemical shift anisotropies for AU-III, while the thermal behavior is investigated by thermogravimetry (TG).     

Kinetic and mechanistic investigations of hydrothermal transformations in zinc phosphates

The room-temperature crystallization of [C(6)N(2)H(18)][Zn(HPO(4))(H(2)PO(4))(2)], an organically templated zinc phosphate containing [Zn(2)(HPO(4))(2)(H(2)PO(4))(4)](4)(-) molecular anions, and its transformation to compounds containing either one- or two-dimensional inorganic components, [C(6)N(2)H(18)][Zn(3)(H(2)O)(4)(HPO(4))(4)], [C(4)N(2)H(12)][Zn(HPO(4))(2)(H(2)O)], or [C(3)N(2)H(6)][Zn(4)(OH)(PO(4))(3)], under hydrothermal conditions were studied in-situ using energy-dispersive X-ray diffraction. The ability to collect data during reactions in a large volume ( approximately 23 mL) Teflon-lined autoclave under real laboratory conditions has allowed for the elucidation of kinetic and mechanistic information. Kinetic data have been determined by monitoring changes in the integrated peak intensities of Bragg reflections and have been modeled using the Avrami-Erofe'ev expression. The crystallization of [C(6)N(2)H(18)][Zn(HPO(4))(H(2)PO(4))(2)] is a diffusion-controlled process, while nucleation is increasingly more important in determining the overall rate of the formation of [C(6)N(2)H(18)][Zn(3)(H(2)O)(4)(HPO(4))(4)], [C(4)N(2)H(12)][Zn(HPO(4))(2)(H(2)O)], and [C(3)N(2)H(6)][Zn(4)(OH)(PO(4))(3)]. The transformation of [C(6)N(2)H(18)][Zn(HPO(4))(H(2)PO(4))(2)] to [C(4)N(2)H(12)][Zn(HPO(4))(2)(H(2)O)] and [C(3)N(2)H(6)][Zn(4)(OH)(PO(4))(3)] occurs via a dissolution-reprecipitation mechanism, while the transformation to [C(6)N(2)H(18)][Zn(3)(H(2)O)(4)(HPO(4))(4)] may be the first observation of a direct topochemical conversion of one organically templated solid to another under hydrothermal conditions.     

Synthesis and Structure of a Novel 3-Fold Interpenetrating Three-dimensional Coordination Polymer：[Ni（Hbyip~（2-））（bix）_（0.5）（H_2O）]_n

A three-dimensional coordination polymer,[Ni(Hbyip2-)(bix)0.5(H2O)]n,has been hydrothermally synthesized.Each Ni2+ ion is five-coordinated by three carboxylate O atoms from three different 5-(benzoic acid-4-yldiazenyl)isophthalate(Hbyip2-) anions,one N atom from one 1,4-bis(imidazol-1-ylmethyl)benzene(bix) ligand and one O atom from an aqua ligand displaying a distorted square-pyramid.Each Ni atom is defined by three Hbyip2-anions and each Hbyip2-anion adopts a tris(mono-dentate) ligand coordinating to three Ni2+ ions affording a 36-membered inorganic ring.These rings are further arranged into an undulated two-dimensional layer parallel to the(101) plane.Adjacent two-dimensional networks are linked by bix ligands into a three-dimensional {63,83}{63} framework with a large channel(ca.26.3 × 13.6) along the [100] direction.Each individual {63,83}{63} network interpenetrates with two others in a parallel fashion to generate a 3-fold interpenetrating network.     

A new type of entanglement involving one-dimensional ribbons of rings catenated to a three-dimensional network in the nanoporous structure of [Co(bix)2(H2O)2](SO4).7H2O [bix = 1,4-bis(imidazol-1-ylmethyl)benzene

Co(II) sulfate reacts with the flexible ligand 1,4-bis(imidazol-1-ylmethyl)benzene (bix) to yield the coordination network [Co(bix)2(H2O)2](SO4).7H2O, containing polymeric ribbons of rings which penetrate and catenate a 3D single frame of the CdSO4 topology, to produce an open-channel entangled architecture with nanoporous behaviour.     

A self-catenated network containing unprecedented 0D + 2D → 2D polycatenation array

Herein, we report a new acylamide ligand and its application in the construction of a metal-organic framework. The resultant acylamide metal-organic framework, namely [Zn(2)(L)(OH)(btc)](n) (1, L = N(1),N(4)-bis(pyridin-3-ylmethyl) naphthalene-1,4-dicarboxamide, H(3)btc = benzene-1,3,5-tricarboxylic acid), was obtained by hydrothermal synthesis. The outstanding structural feature of it is the 0D + 2D → 2D polycatenation array containing a self-catenated feature which has never previously been observed. To the best of our knowledge, the coexistence of self-catenation and polycatenation phenomena is highly exceptional.     

Reversible anion exchanges between the layered organic-inorganic hybridized architectures: syntheses and structures of manganese(II) and copper(II) complexes containing novel tripodal ligands

Six noninterpenetrating organic-inorganic hybridized coordination complexes, [Mn(3)(2)(H(2)O)(2)](ClO(4))(2).2 H(2)O (5), [Mn(3)(2)(H(2)O)(2)](NO(3))(2) (6), [Mn(3)(2)(N(3))(2)].2 H(2)O (7), [Cu(3)(2)(H(2)O)(2)](ClO(4))(2) (8), [Mn(4)(2)(H(2)O)(SO(4))].CH(3)OH.5 H(2)O (9) and [Mn(4)(2)](ClO(4))(2) (10) were obtained through self-assembly of novel tripodal ligands, 1,3,5-tris(1-imidazolyl)benzene (3) and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (4) with the corresponding metal salts, respectively. Their structures were determined by X-ray crystallography. The results of structural analysis of complexes 5, 6, 7, and 8 with rigid ligand 3 indicate that their structures are mainly dependant on the nature of the organic ligand and geometric need of the metal ions, but not influenced greatly by the anions and metal ions. While in complexes 9 and 10, which contain the flexible ligand 4, the counteranion plays an important role in the formation of the frameworks. Entirely different structures of complexes 5 and 10 indicate that the organic ligands greatly affect the structures of assemblies. Furthermore, in complexes 5 and 6, the counteranions located between the cationic layers can be exchanged by other anions. Reversible anion exchanges between complexes 5 and 6 without destruction of the frameworks demonstrate that 5 and 6 can act as cationic layered materials for anion exchange, as determined by IR spectroscopy, elemental analyses, and X-ray powder diffraction.     

Syntheses and structures of two chiral zincophosphite compounds: [Zn(C8H8N2)(HPO3)] and (C6H13N2)[Zn3(C6H12N2)(HPO3)3(H2PO3)

Employing achiral organic amines (2-methylbenzimidazole and 1,4-diazabicyclo[2.2.2]octane) as the structure-directing agent and ligand, two chiral zincophosphites, [Zn(C(8)H(8)N(2))(HPO(3))] 1 and (C(6)H(13)N(2))[Zn(3)(C(6)H(12)N(2))(HPO(3))(3)(H(2)PO(3))] 2, have been hydro(solvo)-thermally synthesized, crystallizing in the chiral space group P2(1)2(1)2(1). Single-crystal structural analysis reveals that compound 1 consists of alternating ZnO(3)N and HPO(3) units exhibiting a neutral one-dimensional chiral chain. Interestingly, the organic ligands interact with the inorganic chain via hydrogen-bonds in hydrogen-bonded helix fashion. Compound 2, a three-dimensional chiral open framework with 16-MR channels, is formed by the distorted {Zn(3)P(4)} secondary building unit (SBU). The organic amine molecules play dual roles as both ligands and countercations.     

Chirality transfer from guest chiral metal complexes to inorganic framework: the role of hydrogen bonding

The structure elucidation of a new zinc phosphate [Co(II)(en)(3)][Zn(4)(H(2)PO(4))(3)(HPO(4))(2)(PO(4))(2 H(2)O)(2)] (1) reveals that the racemic cobalt complex templates the zinc phosphate framework in such a way that the local C(2) point symmetry of the structural motif of the inorganic framework conforms with that of the cobalt complex pairing with it, in essence transferring its chirality to the inorganic host. An analysis of hydrogen bonding between the guest molecules and the inorganic host framework reveals that hydrogen bonding is responsible for the stereospecific structural arrangement. Upon examining previously reported chiral metal-complex-templated structures of metal phosphates, it is revealed that such hydrogen bonding is the common origin for inducing chirality transfer in metal-phosphate frameworks templated with chiral metal complexes. Crystal data of 1: orthorhombic, Pbcn (no. 60), a=10.4787(8) A, b=20.0091(14) A, c=14.9594(10) A, and Z=2.     

1D helix, 2D brick-wall and herringbone, and 3D interpenetration d10 metal-organic framework structures assembled from pyridine-2,6-dicarboxylic acid N-oxide

Five novel interesting d(10) metal coordination polymers, [Zn(PDCO)(H2O)2]n (PDCO = pyridine-2,6-dicarboxylic acid N-oxide) (1), [Zn2(PDCO)2(4,4'-bpy)2(H2O)2.3H2O]n (bpy = bipyridine) (2), [Zn(PDCO)(bix)]n (bix = 1,4-bis(imidazol-1-ylmethyl)benzene) (3), [Zn(PDCO)(bbi).0.5H2O]n (bbi = 1,1'-(1,4-butanediyl)bis(imidazole)) (4), and [Cd(PDCO)(bix)(1.5).1.5H2O]n (5), have been synthesized under hydrothermal conditions and structurally characterized. Polymer 1 possesses a one-dimensional (1D) helical chainlike structure with 4(1) helices running along the c-axis with a pitch of 10.090 Angstroms. Polymer 2 has an infinite chiral two-dimensional (2D) brick-wall-like layer structure in the ac plane built from achiral components, while both 3 and 4 exhibit an infinite 2D herringbone architecture, respectively extended in the ac and ab plane. Polymer 5 features a most remarkable and unique three-dimensional (3D) porous framework with 2-fold interpenetration related by symmetry, which contains channels in the b and c directions, both distributed in a rectangular grid fashion. Compounds 1-5, with systematic variation in dimensionality from 1D to 2D to 3D, are the first examples of d(10) metal coordination polymers into which pyridinedicarboxylic acid N-oxide has been introduced. In addition, polymers 1, 4, and 5 display strong blue fluorescent emissions in the solid state. Polymer 3 exhibits a strong SHG response, estimated to be approximately 0.9 times that of urea.     

以樟脑酸及咪唑基化合物为配体的锌配合物的合成、晶体结构及荧光性质

以硝酸锌、樟脑酸(H2CAM)和1,2-二咪唑基二甲苯(obix)或4,4′-二咪唑基二甲联苯(bimb)为原料,在水热条件下得到2个结构不同的配位聚合物[Zn(obix)(CAM)]n(1)和[Zn(bimb)(CAM)]n(2)。对它们进行了元素分析、红外光谱和热重等分析,并利用X-射线洐射测定了它们的单晶结构。配合物1中2个锌离子通过2个obix配体桥连成一个24元大环,它再通过CAM配体连接成一维管状结构,而配合物2中锌离子通过两种配体桥连成二维层状结构。结果说明了辅助配体在配合物组装过程中起着非常重要的作用。此外还研究了它们的荧光性质。     

Synthesis, Crystal Structure and Photoluminescent Property of a Three-dimensional Zinc（Ⅱ） Coordination Polymer: [Zn1.5（PDB）（bix）0.5（μ2-OH）]2n

A new metal-organic coordination polymer [Zn1.5(PDB)(bix)0.5(μ2-OH)]2n 1 (H2PDB = pyridine-3,4-dicarboxylic acid, bix = 1,4-bis(imidazol-1-ylmethyl)-benzene) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P2/c with a = 7.411(2), b = 7.848(3), c = 25.048(8), V = 1451.8(8)3, C28H22N6O10Zn3, Mr = 798.63, Dc = 1.827 g/cm3, μ(MoKα) = 2.529 mm-1, F(000) = 804, Z = 2, the final R = 0.0440 and wR = 0.1035 for 1952 observed reflections (I > 2σ(I)). It exhibits a three-dimensional framework structure. Moreover, its luminescent property has been investigated in the solid state.