| Coordination polymers ?CPs? or metal-organic frameworks ?MOFs? are crystalline materials constructed from metal ions or clusters bridged by organic ligands to form one-, two-, or three-dimensional infinite networks. Because of the various structures and unique properties, CPs have widely utility in the chemistry, material and bioscience. In this paper, we designed and synthesized a new ligand L1 ?L1= 3,6-di?3-imidazolyl?benzene-1,2-diamine?. Through the introduction with four V-shaped dicarboxylate ligands, five amino-functionalized complexes 1-5 were generated by solvothermal reaction. Four complexes 6-9 were synthesized in solvothermal reaction through the in situ cycloaddition synthesis from L1 and three aldehydes compounds, respectively. Complexes 1-9 were characterized by elemental analysis ?EA?, infrared spectra ?IR?, single-crystal X-ray diffraction, powder X-ray diffraction measurements?XRD?, thermogravimetric analysis ?TGA? and fluorescence spectra.1. Three new amino-functionalized complexes,{[Cd?L1?1.5?HIP?]·?H2O?}n?1?, {[Cd2?L1??ABA?2?H2O?]·?H2O?2}n ?2?,{[Cd?L1?0.5?IBG?]·?H2O?2}n ?3? ?H2HIP= 5-hydroxyisophthalic acid, H2ABA= bis?4-carboxylphenyl?amine, H2IBG= isophthaloylbisglycine?, were synthesized through the reaction of Cd?NO3?2·4H2O, LI and three V-shaped dicarboxylate ligands, respectively. Complex 1 crystallizes in a mononuclear structure with a 3D hxg-d net Complex 2 crystallizes in a tetranuclear fashion with a layer structure. Complex 3 shows an infinite rod-shaped secondary building unit ?SBU? structure. It implies that the structural diversity in assembly process is determined by the flexibility of dicarboxylate ligands. Dicarboxylate ligand with more flexibility intends to chelate more metal nucleus.2. Two new amino-functionalized complexes,{[Zn?PPDA??Ll?]-3H2O}n ?4? and {[Zn2?IBG??L1?]·2H2O}n ?5? ?H2PPDA= 4,4'-?perfluoropropane-2,2-diyl?dibenzoic acid, H2IBG= isophthaloylbisglycine?, were synthesized through the reaction of Zn?NO3?2·6H2O, L1 and two V-shaped dicarboxylate ligands, respectively. Complexes 4 and 5 all crystallizes in a mononuclear structure. Complex 4 crystallizes in triclinic crystal system with P21/c space group. Complex 5 crystallizes in the monoclinic crystal system of C2/c space group. Comparing with the emission spectra of free ligand, complexes 4-5 are all pronounced red-shifted.3. Four complexes,{[Cd?L2??HIP?]·?H2O?2}n ?6?,{[Cd?L2??AIP?]·?H2O?2}n ?7?, [Cd?L3?2]n ?8? and{[Cd?L4??HIP?]·?H2O?2}n ?9?, were synthesized through in situ cycloaddition synthesis of Cd?NO3?2·4H2O, L1 and three aldehydes compounds, respectively. L2, L3 and L4 were generated by the in situ cycloaddition synthesis of L1 and terephthalaldehyde,4-pyridinecarboxaldehyde and glyoxal, respectively. Complexes 6-9 have very good thermal stability, and the decomposition of the frameworks of 8 occurred at about 520 ?. Comparing with the emission spectra of free ligand, these complexes are all pronounced red-shifted, which originated from the expansion of the ?-conjugation system of ligands and ligand-to-metal charge transfer ?LMCT?. This is the first example of construction of CPs through the in situ cycloaddition synthesis from o-phenylenediamine derivative and aldehydes. |
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