| The increasing interest in coordination polymers with multi-carboxylate/sulfonate is ascribed to the structural diversity and potential applicatios （catalyst reaction, gas-storage, magnetic, optical and nonlinear optical properties etc.）. The reasonable choice of the linker- multidenate organic aromatic polycarboxylate ligands without/with multi-functional （-NO3,-N, -OH, -SO3H）, nodes—metal ions/metal cluster （transition metal and rare-earth metal） as nodes and pillar—N-containing heterocyclic ligands （from rigid to flexible）, gives rise to a series of coordination polymers （zero-dimensional, one-dimensional, two-dimensional and three-dimensional）. In this paper, H4btc, btc-NO2 and IHQS have been carried out to the synthesis of three series of carboxylate/sulfonate coordination polymers, and the factors that influence the final structures are investigated at the same time. In this paper 18 novel compounds have been yieled by assembly reactions of organic aromatic ligands, and further characterized by elemental analyses, X-ray single crystal diffraction, FTIR, XRD, thermogravimetric analyses, magnetism and fluorescence spectra.1. Four coordination compounds have been hydrothermally synthesized based on btc-NO2 ligand as“linker”, the intended ancillary N-heterocyclic ligands, 4,4’-bpy, 1,3-bis（1,2,4-triazol-1-yl）propane （btp）, 1,6-bis（1,2,4-triazol-1-yl）hexane（bth） as“pillar”. The common building unit of [Cu2（ipO-NO2）2], with ipO-NO2 representing the deprotonated 5-NO2-2-hydroxyisophthalate （ipO-NO2）, was formed in situ from the reaction of 5-NO2-1,2,3-benzenetricarboxylic acid （H3btc-NO2） with CuⅡ. Despite the different structures, the overall magnetic interactions existing in these compounds were found to be invariably antiferromagnetic. Compound 1 exhibited a three-dimensional （3D） wave-like structure, while 2 displays a 1D alternate chain-like structure. Compounds 3 and 4 were discrete polynuclear species featuring a hexa- and a nona-nuclear core, respectively. Furthermore, a systematic research on the effect factors that influence in situ metal-ligand of CuⅡand btc-NO2 ligand, was presented herein. In addition, We present herein a systematic research on this reaction based on btc-NO2, which clarifies the same conclusion that the hydroxylation requires CuⅡions as the oxidant, and the decarboxylate procedure can happen under the high temperature and less acidic condition.{CuⅡCuI（ipO-NO2）（4,4’-bpy）}n （1）[Cu6Ⅱ（ipO-NO2）4btp（H2O）8]·6H2O （2）Cu（12）Ⅱ（ipO-NO2）8（bth）4（H2O）10·2H2O （3）Cu18Ⅱ（ipO-NO2）12（btp）3（H2O）18（EtOH）6·13H2O （4） 2. Four new coordination compounds have been hydrothermally and conventionally synthesized based on btc-NO2 ligand and N-containing heterocyclic ligands （4,4’-bpy and phen） with CuⅡ. Compound 5 exhibits the intriguing 3D framework constructed from both binuclear [CuⅡ2（COO）2] unit （and mononuclear [CuO4N2] unit, displaying （3,4,6）-connected （4.6.8）2（62.84） （42.62.810）.12） topology. 6 displays interesting 2D ladder-layered network constructed from trinuclear [Cu3（μ2-OH2）2] unit and mononuclear [Cu（Hbtc-NO2）] unit as the linking nodes, showing （3, 6）-connected （42.6）2（46.66.83） nets. Compounds 7 and 8 are zero dimensional single molecule structure which are further cross-packed byπ···πinteractions.[Cu3Ⅱ（btc-NO2）2（4,4’-bpy）2（H2O）2]·2H2O （5）[Cu5Ⅱ（btc-NO2）2（Hbtc-NO2）2（4,4’-bpy）2（μ2-OH2）2（H2O）8]·4H2O （6）[CuⅡ（Hbtc-NO2）（phen）]·2H2O （7）[Cu2Ⅱ（Hbtc-NO2）（phen）4]·8H2O·（NO3-）2 （8）Two new coordination compounds have been hydrothermally synthesized based on btc-NO2 ligand and N-containing heterocyclic ligands （4,4’-bpy, bpp） with CuⅡ, ZnⅡ. The structure of 9 exhibits the intriguing 3D framework constructed from both binuclear [Co2Ⅱ（COO）2] unit and mononuclear [CoO4N2] unit, displaying （3,4,6）-connected （4.6.8）2（62.84）（42.68.83.102） topology. A rare U-shaped [Zn7O4（O2C）12N4] secondary building unit with four crystallographically distinct zinc（Ⅱ） ions is found in 10, together with double parallel btc-NO2 anions and bpp flexibility ligands as links, resulting in an eight-connected heptanuclear-based uninodal 3D framework with 424.64 topology. Compounds 11 has been conventionally synthesize based on H4btc and dmap ligands with AgI. The binuclear [Ag2O4] cluster is linked to four clusters by four H4btc ligands, generating 2D rhombic （4,4） networks. A 3D network is accomplished throuth non-covalent interactions. There are many factors that influence the final products, such as temperature, N-containing heterocyclic ligands and metal-ligand ratio. Moreover, the magnetic properties of compounds 5, 6, 9 and the luminescent property of 10 have been investigated as well.Co3Ⅱ（btc-NO2）2（4,4’-bpy）3（H2O）2 （9）Zn7Ⅱ（btc-NO2）4（bpp）2（μ3-OH）2（μ-OH2）2 （10）[Ag2（Hbtc）]·（Hdmap） （11）3. Seven new coordination compounds have been hydrothermally and conventionally synthesized based on IHQS ligand and 4,4’-bpy with Cu（Ⅱ）、Co（Ⅱ）、Ni（Ⅱ） and La（ⅡI）. Compound 12 exhibits one dimensional infinite chain-like structure and compound 13 displays the one dimensional sheet-like framework, where the copper bichains are bridged by 4,4’-bipy ligands. Compounds 14 and 15 are zero dimensional single network which are further cross-linked into 3D networks throuth non-covalent interactions. There are three directions 1D chain in 16, adjacent chains are rotated by 60°to produce virtualtriangle. Compounds 17 and 18 displays the one dimensional sheet-like frameworks, which are further cross-linked into hither networks throuth non-covalent interactions. The results proved that the weak interactions of the iodo, sulfonato and quinoline moieties are important effects on supporting supermolecule. The magnetic properties of 12 and 13 are discussed, and there is presence of antiferromagnetic interactions in 12 but ferromagnetic interactions in13.Ni（IHQS）（4,4’-bpy）0.5（H2O）2 （12）Cu（IHQS）（4,4’-bpy）0.5H2O （13）[Co2（IHQS）2（H2O）6]·4H2O （14）[Zn2（IHQS）2（H2O）6]·4H2O （15）[Ni（SO4）（4,4’-bpy）2（H2O）3]·2H2O （16）[La2（IHQS）4（H2O）8]·5H2O （17）[La（IHQS）2 （H2O）3]·5H2O·（4,4’-bpy） （18）... |
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