A novel pillared-layer framework with a （52.6）（53.63.73.8） Schlaifli symbol, [Mn（H2O）（Htrc）（Hbtc）]n （1）, was prepared by the reaction of 1,2,4-triazole （Htrz）, 1,3,5-benzene- tricarboxylic acid （H3btc）, and MnII salt and structurally and magnetically characterized. It crystallizes in the orthorhombic system, space group P212121 with a = 7.1618（5）, b = 9.0356（6）, c = 10.9740（13） A, V = 1292.54（15） A3, Dc = 1.799 g/cm3, Mr = 350.15, Z = 4, F（000） = 708, p = 1.064 mm-1, and the final R = 0.0177 and wR = 0.0462 for 2273 observed reflections with I〉 2σ（I）. The unique octahedral Mnn ion in 1 is periodically linked into a two-dimensional （2D） magnetic layer by p2-N1, N4-Htrz and syn, anti-COO of doubly deprotonated Hbtc2- anion, which is further supported by the phenyl backbone of Hbtc2- ligand to generate a 3D pillared-layer framework. Magnetically, complex 1 displays an antiferromagnetic ordering below 5.0 K due to the cooperative antiferromagnetic couplings mediated by the mixed heterobridges within the magnetic layer.
A new magnetic MOF with cyclic triazolate and linear azido mediators, [Co2（trz）3fN3）], 1 （trz- = 1,2,4-triazolate）, was hydrothermally synthesized and structurally and magnetically characterized. 1 crystallizes in the rhombohedral P63/mmc space group with a = b = 10.0716（17）, c = 7.5860（14） A, V = 666.4（2） A3, Dc = 1.814 g/cm3, Mr = 364.09, Z = 2, F（000） = 360,μ = 2.499 mm-1, the final R = 0.0676 and wR = 0.1952 for 229 observed reflections with 1 〉 20（/）. Complex 1 consists of linear {Co（trz）3}n chains passing through a C6 rotation axis, which are interconnected with tetrahedral Con ion by μ3-trz- ligands into a hexagonal three-dimensional antiferromagnetic framework.
Two 4,5-dichlorophthalate-based metal complexes, {[Cu（bipy）（dcpa）].H2O}n, （1） and {[Cu2Coipy）2（Hdcpa）3]·H2O·C2H5OH.Hdcpa} （2, H2dcpa = 4,5-dichlorophthalic acid and bipy = 2,2＇-bipyridine）, were synthesized and characterized structurally and magnetically. Complex 1 is of orthorhombic system, space group Fdd2 with a = 20.5821（8）, b = 20.9013（12）, c = 17.0270（7） A, V= 7324.9（6） A3, Dc = 1.707 g/cm3, Mr = 470.74, Z = 16, F（000） = 3792, p = 1.519 mm^-1, the final R = 0.0223 and wR = 0.0549 for 9239 observed reflections with I〉 2σ（I）. Complex 2 crystallizes in triclinic, space group P1 with a = 14.1439（12）, b = 14.2981（12）, c = 15.1054（14） A, a = 72.121（2）, β = 77.703（2）,γ = 81.829（2）°, V= 2830.9（4） A3, Dc = 1.689 g/cm3, M,. = 1439.55, Z = 2, F（000） = 1452,μ = 1.207 mm^-1, the final R = 0.0536 and wR = 0.0981 for 16422 observed reflections with 1 〉 2σ（I）. Complex 1 exhibits a diamond-like framework with centrosymmetric binuclear subunits extended by pairs of doubly deprotonated dcpa2- linkers. By contrast, 2 is an asymmetric binuclear entity bridged by carboxylate group of mono deprotonated Hdcpa- ligands. Weak anti- and ferromagnetic interactions are respectively mediated in the carboxylate aggregated binuclear subunits of 1 and 2.
Two new 1-naphthoate-based Pb（Ⅱ） complexes, [Pb（phen）（NA）2]n 1 and [Pb（bpp）（NA）2]n 2 （NA = 1-naphthoate, phen = 1,10-phenanthroline, and bpp = 1,3-bi（4-pyri- dyl）propane）, were hydrothermally synthesized and structurally characterized. 1 is of monoclinic system, space group C2/c with a = 28.114（3）, b = 10.9601（10）, c = 8.6843（8） , β = 93.3760（10）°, V = 2671.3（4） 3, Dc = 1.814 g/cm3, Mr = 729.73, Z = 4, F（000） = 1416, μ = 6.360 mm-1, the final R = 0.0346 and wR = 0.0948 for 2184 observed reflections with I 〉 2σ（I）. Complex 2 crystallizes in monoclinic, space group C2/c with a = 26.491（2）, b = 8.7773（6）, c = 27.893（2） , β = 113.3020（10）°, V = 5956.8（8）3, Dc = 1.668 g/cm3, Mr = 747.78, Z = 8, F（000） = 2928, μ = 5.706 mm-1, the final R = 0.0211 and wR = 0.0493 for 3677 observed reflections with I 〉 2σ（I）. Both complexes present one-dimensional （1-D） zigzag chains extended by anionic NA linkers for 1 and bridged by neutral bpp connectors for 2, which are further aggregated into 2-D supramolecular networks by interchain π···π stacking interactions. In addition, the two solid-state complexes exhibit different strong emissions at room temperature, suggesting their potential applications as fluorescence materials.
