Nine new coordination polymers, namely, [Mn(2)(L)(H(2)O)(4)].H(2)O (1), [Cd(L)(0.5)(H(2)O)] (2), [Zn(5)(L)(2)(mu(3)-O)(2)(H(2)O)(4)].2H(2)O (3), [Zn(4)(L)(2)(mu(3)-O)(2)][Zn(H(2)O)(5)].2H(2)O (4), [Zn(2)(L)(biim-4)(0.5)(H(2)O)(3)].H(2)O (5), [Cd(2)(L)(bpy)(H(2)O)].2H(2)O.0.5(CH(3)CH(2)OH) (6), [Cu(2)(H(2)L)(2)(bpy)(2)] (7), [Cu(2)(L)(bpy)(H(2)O)] (8), and [Cu(2)(L)(bpy)(1.5)(H(2)O)(2.5)] (9), where H(4)L = 1,2,3,4-benzenetetracarboxylic acid, biim-4 = 1,1'-(1,4-butanediyl)bis(imidazole), and bpy = 4,4'-bipyridine, have been synthesized under hydrothermal conditions. Compound 1 displays a rare trinodal (3,4,7)-connected (4(2).6)(4(5).6)(4(7).6(8).8(6)) topology. 2 possesses an alpha-Po net. 3 is a novel 3D framework based on pentanuclear Zn(II) clusters. By adjustment of the pH values of the reaction mixture of 3 with a Na(2)CO(3) solution, a structurally different compound, 4, was obtained, which exhibits a 3D porous framework with the [Zn(H(2)O)(6)](2+) cations located in the channels. 5 is an unusual example of a trinodal (3,5)-connected network with a Schlafli symbol of (4(2).6)(6(2).8)(4(2).6(2).8(5).10), whereas 6, containing tetranuclear Cd(II) clusters, shows a rare (4,6)-connected (4(4).6(2))(2)(4(4).6(10).8) topology. 7 exhibits a unique polythreading network, while 8 displays a scarce trinodal (3,4,5)-connected self-penetrating network. In comparison with 8, the chiral compound 9 possesses an unprecedented tetranodal (2,4)-connected (7)(7(5).11)(6(2).7(3).8)(2)(6.7(4).10)(2) topology. The effects of the carboxylate ligands, the pH values, the reaction temperatures, the central metals, and the neutral ligands were elucidated. The IR spectra, thermogravimetric analysis, and luminescent properties for the compounds were also investigated.
Seven coordination polymers, namely [Zn(BPTC)0.5(L1)0.5(H2O)] (1), [Zn2(BPTC)(L2)]·H2O (2), [Zn2(BPTC)(L3)2]·3H2O (3), [Zn2.5(BPTC)(L4)(OH)(H2O)] (4), [Zn2(BPTC)(L5)(H2O)2]·3H2O (5), [Cd2(BPTC)(L5)(H2O)]·H2O (6), and [Cd(BPTC)0.5(L6)]·H2O (7), where L1 = 4,4′-bis(imidazol-1-ylmethyl)bibenzene, L2 = 4,4′-bis(imidazol-1-ylmethyl)benzene, L3 = 1,4-bis(imidazol-1-yl)butane, L4 = 1,4-bis(2-ethyl-imidazol-1-yl)butane, L5 = 1,3-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene, L6 = 1,2-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene, and BPTC = 3,3′,4,4′-benzophenone tetracarboxylate ligand, have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. The structure of 1 exhibits a (4,6)-connected network with a (44·62)(44·610·8) topology formed by L1 ligands connecting BPTC−Zn sheets. The structure of 2 is a chiral 3D network in which there exists a Zn−O helical chain which may transmit the chirality to the whole framework. In compound 3, multicarboxylate ligands link L3−metal helical chains to generate a layer which is further connected by intermolecular H bonds to form a 3D supramolecular structure. In compound 4, the L4−Zn sheets are connected by BPTC pillars to generate a 3D framework with a distorted α-Po topology. Compound 5 shows infinite chains. Compound 6 shows two kinds of novel infinite chains which are linked by π−π stacking interactions to form 2D supramolecular sheets. Compound 7 is a (3,4)-connected framework with a (62·8)2(62·84) topology. The structural differences among 1–4 indicate the importance of the flexibility of the ligands (L1−L4) for the framework formation of the coordination polymers. By varying the angular feature of the ligands (L5 and L6), compounds 5–7 have been separated completely. In additon, the luminescent properties of these compounds are discussed.
Eight new metal-organic frameworks based on the tetrakis(imidazole) ligand tetrakis(imidazol-1-ylmethyl)methane (L), namely, [Zn 2 (L) O (8), where H 2 L 1 = 1,4-benzenedicarboxylic acid, H 3 L 2 =1,3,5-benzenetricarboxylic acid, and H 4 L 3 =1,2,4,5-benzenetetracarboxylic acid, have been synthesized under hydrothermal conditions. Compounds 1 and 2 were isolated by the reactions of L with inorganic SO 4 2anions. Compound 1 displays a 2-fold interpenetrated PtS net. Compound 2 possesses a binodal (4,6)-connected topology with the Schl€ afli symbol of (3 3 4 3 5 3 3 6)(3 2 3 4 3 5 4 3 6 7 3 7). Compounds 3-8 have been obtained by the reactions of L with organic carboxylate ligands. Compound 3 shows a trinodal (3,4)-connected topology with the Schl€ afli notation of (6 6 )(6 5 3 8)(6 3 ). Compound 4 is isostructural with 3. The compound 5 is a binodal (3,4)-connected two-dimensional (2D) net with the the Schl€ afli notation of (6 2 3 8) (4 3 6 4 3 8). 6 shows a trinodal (3,4)-connected framework with the Schl€ afli symbol of (4 3 8 2 ) 2 (4 2 3 8 4 )(8 4 3 12 2 ). Compound 7 exhibits a pentanodal net with the Schl€ afli symbol of (4 3 6 3 8 4 )(4 2 3 6 4 )(4 2 3 8 4 )(4 2 3 8 3 3 10)(4 3 6 2 3 8 3 ). Compound 8 is a rare 4-connected 2D net with the Schl€ afli symbol of (4 3 3 6 3 ). The influence of the metal atoms and ligands on the structures of the coordination polymers has been discussed. The infrared spectra, thermogravimetric analysis, and luminescent properties were also investigated for the compounds.
Ten new coordination polymers constructed from two structurally related ligands, 1,1 0 -(1,5-pentanedidyl)bis-(imidazole) (biim-5) and 2,2 0 -bis(1H-imidazolyl)ether (BIE), have been synthesized: 10), where H 2 L1 = 1,2-benzenedicarboxylic acid, H 2 L2 = 1,3-benzenedicarboxylic acid, H 2 L3 = 5-OH-1,3-benzenedicarboxylic acid, H 2 L4 = DL-camphoric acid, H 4 L5 = 1,2,3,4-butanetetracarboxylic acid, H 4 L6 = 4,4 0 -oxidiphthalic acid, H 4 L7 = 4,4 0 -(hexafluoroisopropylidene)diphthalic acid, and H 4 L8=1,2,3,4-benzenetetracarboxylic acid. Compounds 1 and 4 display the same 2D layer structures with 6 3 -hcb nets, but in 4 the water tetramers extend the layers to a 3D supramolecular framework by intermolecular hydrogen bonds. Compound 2 is an uncommon example of 2D double layers with the Schl€ afli symbol of (4 2 3 6 3 3 8). 3 shows a 2D sql net with large open windows, while 5 exhibits a rare 3,4-connected (8 3 ) 2 (8 5 3 10) topology. The crystal structures of 6 and 7 are close to being isostructural with a scarce (3 2 3 6 2 3 7 2 )(3 2 3 4 3 6 2 3 7) 2 topology. 8 contains two kinds of chiral layers, one left-handed and the other right-handed, with a unique topological type of (5 2 3 6 4 )(5 3 3 6 2 3 7) 2 . Compound 9, related by a pseudocenter of inversion, possesses a 3D porous framework with a (3,4)-connected (4 3 10 2 ) 2 (4 2 3 10 4 )-dmd-net. 10 shows a 1D chain structure. The structural and topological differences of these ten compounds indicate that the polycarboxylate ligands play important roles in producing novel frameworks and topologies of the coordination complexes. The infrared spectra and thermogravimetric and luminescent properties were also investigated for the compounds.
Reactions of Ph(3)SnOH or Ph3SnCl with aryl arsonic acids RAsO3H2, where R=C6H5 (1), 2-NH2C6H4 (2), 4-NH2C6H4 (3), 2-NO2C6H4 (4), 3-NO2C6H4 (5), 4-NO2C6H4 (6), 3-NO2-4-OHC6H3 (7), 2-ClC6H4 (8) and 2,4-Cl2C6H3 (9), gave 18 Sn-O cluster compounds. These compounds can be classified into four types: type A: [{(PhSn)3(RAsO3)3(mu3-O)(OH)(R'O)2}2Sn] (R=C6H5, 2-NH2C6H4, 4-NH2C6H4, 2-NO2C6H4, 3-NO2C6H4, 2-ClC6H4, 2,4-Cl2C6H3, and 3-NO2-4-OHC6H3; R'=Me or Et); type B: [{(PhSn)3(RAsO3)(2)(RAsO3H)(mu3-O)(R'O)2}2] (R=4-NO2C6H4, R'=Me); type C: [{(PhSn)3(RAsO3)3(mu3-O)(R'O)3}2Sn] (R=2,4-Cl2C6H3, R'=Me); type D: [{Sn3Cl3(mu3-O)(R'O)3}(2)(RAsO3)4] (R=2-NO2C6H4 and 4-NO2-C6H4; R'=Me or Et). Structures of types A and B contain [Sn3(mu3-O)(mu2-OR')2] building blocks, while in types C and D the stannoxane cores are built from two [Sn3(mu3-O)(mu2-OR')3] building blocks. The reactions proceeded with partial or complete dearylation of the triphenyltin precursor. These various structural forms are realized by subtle changes in the nature of the organotin precursors and aryl arsonic acids. The syntheses, structures, and structural interrelationship of these organostannoxanes are discussed.
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