Three new coordination polymers, [Ag4(H2bpz)4(SO4)2]·H2O (1), [Ag2(H2bpz)2(SO4)]·3H2O (2), and [Ag3(H2bpz)4](SO4)2/3(OH)5/3·4H2O (3) have been solvothermally synthesized with Ag2SO4 and flexible ligand 3,3',5,5'-tetramethyl-4,4'-bipyrazole (H2bpz) in different solvents and temperatures. Complex 1 is a 2-fold interpenetrated three-dimensional (3D) framework with an uncommon (3,5)-connected hms topology. Complex 2 is a structural isomer of 1 and shows a three-connected 2D ths net consisting of interesting 3-fold and 2-fold heterochiral helical chains. Complex 3 discloses a grid layer structure, containing heterochiral helical chains and an unusual meso-helix. More interestingly, three sets of layers in 3 stack in different directions, affording an unprecedented 2D + 2D + 2D → 3D polycatenating cationic framework with 1D + 3D porous systems. In 1-3, H2bpz exhibit exobidentate bridging fashions with wide-ranged interpyrazole tilting angles and changeable coordination configurations, such as cis and trans fashions in 1 and 3 and uniform trans fashion in 2. These lead to the isomeric [Ag(H2bpz)]n arrays of wavelike and helical chains in 1 and 2, respectively. Complexes 1-3 display solid-state photoluminescence stemming from the ligand-centered fluorescent emissions of H2bpz. Because of the highly polar framework, 3 shows excellent adsorption selectivity for CO2 over N2.
Employing an uninvestigated eight N-donor bitriazole ligand, 5'-(pyrazin-2-yl)-2H,4'H-3,3'-bi(1,2,4-triazole) (H2pzbtz), five complexes, {[Zn2(pzbtz)(SO4)(H2O)2]·2H2O}n (), {[Cd(pzbtz)]·3H2O}n (), [Zn3(Hpzbtz)2(SO4)2(H2O)6] (), [Co(Hpzbtz)2(H2O)2] () and {[Co2(pzbtz)2(H2O)2]·4H2O}n (), have been solvothermally synthesised by altering the reaction solvents and temperatures. Complex shows a three-dimensional (3D) framework with a very rare (3,5)-connected fsc-3,5-Cmce-2 topology. Complex exhibits a (4,4)-connected 3D pts framework with 1D channels. Complexes and are discrete trinuclear and mononuclear molecules, respectively. Complex presents a chiral 3D framework based on a novel trinuclear Co3(tr)4 cluster and features an unusual six-connected lcy topology. In the five complexes, H2pzbtz show a very variety of geometrical configurations and coordination modes. Due to the planarity of H2pzbtz, complexes display strong photoluminescence; in particular, features highly selective luminescent sensing for the Cu(2+) ion and nitrobenzene molecule. In addition, shows highly selective adsorption for CO2 over CH4, and exhibits antiferromagnetic exchange interactions among the Co(2+) ions.
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