| Metal-organic coordination polymers (MOCPs) as a newly-identified functional molecule-based materials, have attracted much more attentions because of their flexible tailoring, various topologies and promising applications in hydrogen storage, ion-exchange, adsorption, molecular recognization, catalysts along with optics, electrics, magnetism and enantioselective separation. According to the principle of molecular engineering, it is possible that rational design and synthesis of novel multifunctional materials by selecting certain geometric metal ions and special organic ligands. At the same time, MOCPs can be endowed with multifunctional properties by selecting functional metal ions and organic ligands with functional groups.In this dissertation, we have focused our study on the influence of the metal ions, organic ligands and secondary ligands on the building blocks and structures of MOCPs by the hydrothermal reaction. Twenty-one new coordination compounds have been synthesized by using novel organic ligands and metal ions. The study on synthetic conditions and rules for these new compounds, topological analyses, and the exploration of relationships between structures and properties for these new compounds are also carried out. These compounds have been structurally characterized by elemental analyses, IR, XRPD, TG and single crystal X-ray diffractions. In addition, the thermal stabilities, fluorescent activity and photovoltage transients of these compounds have been studied. These results will be introduced from the following five issues:1. Four novel 3D compounds, [Zn2(BOABA)(L1)(OH)]·2H2O(1), [Zn2(BOABA)(L1)(OH)]·4H2O(2), [Zn3(TMA)2(OH)]·[N(C4H9)4](3), and [Cu2(BTEC)(OH)]·(L1)(4), have been synthesized using the traditional hydrothermal methods, on the basis of 4,5-didanzole-9-wo (L1) ligands, aromatic polycarboxylate ligands with different configurations, and transition metal ions. Compound 1 shows a (3, 6)-connected rutile network constructed by tetranuclear clusters and BOABA ligands. Compound 2 displays a novel (3, 6)-connected network with complex (4.62)2(42.69.84) topology, which is constructed by tetranuclear clusters and BOABA ligands. In 3, the connection between trinuclear zinc clusters (six-connected nodes) and MTA ligands (three connections) results in an infinite 3D (3, 6)-connected network with Schl·fli symbol (4.62) (63) (4.611.83). Compound 4 exhibits a 4, 8-connected scu network that is made of tetranuclear clusters as eight-connected nodes and BTEC as four-connected nodes.2. Four compounds with different dimensionalities, [Cd(BDC)(L2)](5), [Cd2(bpdc)2(L2)2](6), [Cd(oba)(L2)]·H2oba(7), and [Cd(BTEC)0.5(L2)]·(H2O)(8), have been prepared under hydrothermal conditions on the basis of 4,5-didanzole-9-wo-3-methylpyridine (L2) ligands, aromatic polycarboxylate ligands with different configurations, and transition metal ions. In 5 and 6, L2 ligands link with Cd atoms to form the annular units [CdL2]2. These units are further connected through linear aromatic carboxylic acids to construct the (6, 3) sheets. Compound 5 presents a 2D-3D supramolecular network through inclined interpenetration of the (6, 3) sheets. In compound 6, two (6, 3) sheets interpenetrated into a double layer in a parallel way, and then the double layers construct an infinite 2D-3D supramolecular network through the inclined interpenetration. Compound 7 is a helical pillared 2D complex including 1D nanochannels, in which L2 and oba ligands coordinate with Cd atoms in a V-shaped mode. Compound 8 shows a novel (3, 4)-connected network with (83).(85.10) topology constructed by Cd atoms as four-connected nods and BOABA ligands as three-connected nodes.3. Five new compounds, [Zn2(BDC)1.5(L3)]·H2O(9), [Zn2(BDC)0.5(m-BDC)(L3)(H2O)]·H2O(10), [Zn4(m-BDC)4(L3)2(OH)2]·3H2O(11), [Zn2(BTC)(L3)(H2O)]·H2O(12), and [Zn3(TMA)(L3)2 (OH)]·2H2O(13), have been hydrothermally synthesized on the basis of 4,5-didanzole-9-wo-3-acetic acid ligands (L3), aromatic polycarboxylate ligands with different configurations, and transition metal ions. Compound 9 exhibits a five-connected 3D network, which is constructed by L3 and BDC ligands linking with five-connected dinuclear zinc clusters. Compounds 10-12 possess 2D geometries constructed by L3 ligands, different aromatic polycarboxylate ligands, and zinc atoms. Compound 13 demonstrates a novel (3, 6)-connected network with (52.6) (42.55.67.7) topology, which is constructed by trinuclear zinc clusters as four-connected nods and TMA ligands as three-connected nodes.4. Six compounds, [Zn2(OABDC)(OH)](14), [Cd1.5(OABDC)(H2O)2.5]·H2O(15), [Cd2ZnOABDC2(H2O)4]·3H2O(16), [Zn2(OABDC)(4,4'-bpy)(OH)]·3H2O(17), [Cd3 (OABDC)2(4,4'-bpy)2(H2O)7]·2.5H2O(18), and [CdZn2(OABDC)2(4,4'-bpy)2(H2O)4]·H2O(19), have been hydrothermally synthesized on the basis of 5-oxyacetateisophthalic acid (H3OABDC) ligands, 4,4'-bipyridine ligands and different transition metal ions: Compound 14 displays a new 3D framework constructed by three types of helical chains. Compound 15 also prestents a 3D framework, which is constructed from (6, 3) sheets pillared by 1D chains. Compound 16 exhibits a T-shape 2D layer resulted from OABDC ligands linking with Cd atoms. Compounds 17-19 show complex frameworks due to the introduction of bridged 4,4'-bpy ligands. Compound 17 exhibits a novel (3, 8)-connected 3D network, which is constructed from the (3, 6)-connected 2D layers pillared by 4,4'-bpy ligands. Compound 18 shows a noncentrosymmetric interlocked 3D supramolecular network based on intertwining of two kinds of asymmetric helix. Compound 19 displays a novel 3, 4-connected network with (62.8) (6.82) (62.83.10) topology based on OABDC ligands and mixed metals (Zn and Cd).5. Two novel compounds, [Zn3(BTA)6](20) and Zn7(BTA)7(OABDC) (μ3-OH)2(μ2-OH)2·(H2O)(21), have been synthesized under hydrothermal conditions, on the basis of benzotriazole (BTA), H3OABDC ligands and transition metal ions. Compound 20 as a novel chiral coordination polymer with a bikitaite zeolite framework has been constructed from asymmetric tetrahedral building blocks, in which the original chiralities derive from the configurational effect of benzotriazole ligands and transfer to the network through four distinct helical chains. In compound 21, an unprecedented metallophthalocyanine-like subunit, Zn2(μ3-OH)2·[Zn4BTA4], which is constructed fromη3-BTA ligands as fragment ligands, and further linked viaμ2-OH, outer four-connected Zn atoms, and 5-oxyacetateisophthalic acid, to form a novel three-dimensional framework.
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