A new Zn-citrate coordination complex {K[Zn(C6H5O7)(H2O)]}n(1) was synthesi- zed via hydrothermal reaction. In the crystal structure of complex 1, each citrate serves as thequadricdentate ligand coordinating to three Zn(II) ions, forming a zigzag chain, and such chains are further connected into a 3D network by the K+ linkers. Crystal data for complex 1: triclinic, space group Pī, α = 7.3487(9), b = 7.5397(6), c = 9.6772(8) A, α = 76.894(8), β = 68.260(10), γ = 65.155(10)°, V = 450.34(7) ?3 and Z = 2. Other characterizations by elemental analysis, IR, TG and fluorescence were also described.
By using solvothermal method,two novel coordination polymers based on 4-(4-carboxyphen-yl)-1,2,4-triazole(Hcpt) and Zn(Ⅱ) cations,[Zn(cpt)(OH)]_n·n H_2O(FJU-32) and [Zn(cpt)(atrz)]n(FJU-33)(Hatrz = 3-amino-1,2,4-triazolate),were synthesized and characterized by single-crystal X-ray diffraction analyses,elemental analyses,FT-IR and powder X-ray diffraction. FJU-32 crystallizes in monoclinic,space group P21/c with a = 3.7441(3),b = 23.0384(19),c = 11.8562(10) ?,β = 99.069(8)o,V = 1009.91(15) ?3,Dc = 1.898 g/cm3,C_9H_9N_3O_4Zn,Mr = 288.57,F(000) = 916,μ(MoKα) = 2.439 mm^(-1),Z = 4,R = 0.0600 and wR = 0.1306 for 2412 observed reflections(I 〉 2σ(I)),and R = 0.0704 and wR = 0.1349 for all data. FJU-33 crystallizes in monoclinic space group P21/c with a = 12.7483(5),b = 9.9922(3),c = 9.8403(3) ?,β = 100.756(4)°,V = 1231.47(7) ?~3,Dc = 1.816 g/cm^3,C_(11)H_9N_7O_2Zn,Mr = 336.62,F(000) = 680,μ(Cu Kα) = 2.957 mm^(-1),Z = 4,R = 0.0478 and w R = 0.1184 for 2466 observed reflections(I 〉 2σ(I)),and R = 0.0687 and w R = 0.1309 for all data. In FJU-32,Zn(Ⅱ) is coordinated to three μ3-OH groups forming an unprecedented 1D zigzag-like double chain,and the 1D double chains are connected to four neighbouring double chains by the cpt ligands to form an extended 3D porous coordination polymer. In FJU-33,the adjacent [Zn(atrz)] 2D layers are further connected by the cpt ligands via Zn–O coordinated bonds and neighboring interlayer hydrogen-bonding interactions to give rise to an overall 3D pillared layer structure. The neutron triazole group of the cpt ligand has weaker coordination ability than the triazolate anion of atrz ligand. Furthermore,FJU-32 and FJU-33 display high thermal stability up to 300 ℃,and the solid state fluorescence reveals that two new complexes are potential optical materials.
Hierarchically porous materials play an important role in facilitating mass transport and improving efficiency of adsorption and separation processes. In this paper, a new strategy is proposed to realize a hierarchically porous metal-organic framework ([Cu2(OH)(L)]'(DMF)0.8 (FJU-11, H3L=3,5-(4-carboxybenzyloxy)benzoic acid, DMF= N,N-dimethylformamide) via using semi-rigid multi-carboxylic acids. Interestingly, FJU-11 possesses the large adsorption capacities and small isosteric heats toward CO2. The column breakthrough experiment for FJU-11 highlights its potential application in the separation of the flue gas.