A novel pillared-layer framework with a (52.6)(53.63.73.8) Schl fli symbol, [Mn(H2O)(Htrz)(Hbtc)]n (1), was prepared by the reaction of 1,2,4-triazole (Htrz), 1,3,5-benzenetricarboxylic acid (H3 btc), and Mn Ⅱ 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) , V=1292.54(15) 3 , D c=1.799 g/cm3 , Mr=350.15, Z=4, F(000)=708, μ=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 Mn Ⅱ ion in 1 is periodically linked into a two-dimensional (2D) magnetic layer by μ2 -N1 , N4 -Htrz and syn, anti-COO of doubly deprotonated Hbtc 2anion, which is further supported by the phenyl backbone of Hbtc 2ligand 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)3(N3)]n 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) , V = 666.4(2) 3, Dc = 1.814 g/cm3, Mr = 364.09, Z = 2, F(000) = 360, μ = 2.499 mm1, the final R = 0.0676 and wR = 0.1952 for 229 observed reflections with I > 2σ(I). Complex 1 consists of linear {Co(trz)3}n chains passing through a C6 rotation axis, which are interconnected with tetrahedral CoⅡ ion by u3-trz- ligands into a hexagonal three-dimensional antiferromagnetic framework.
Two 4,5-dichlorophthalate-based metal complexes,{[Cu(bipy)(dcpa)]·H2O}n(1)and {[Cu2(bipy)2(Hdcpa)3]·H2O·C2H5OH·Hdcpa}(2,H2 dcpa = 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 α = 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,μ = 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 α = 14.1439(12),b = 14.2981(12),c = 15.1054(14) A,α = 72.121(2),β = 77.703(2),γ = 81.829(2)°,V= 2830.9(4) A3,Dc = 1.689 g/cm3,Mr = 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 I > 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 Hdcpa2- 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.
