Trinuclear Cobalt Based Porous Coordination Polymers Showing Unique Topological and Magnetic Variety upon Different Dicarboxylate-like Ligands

One-pot solvothermal self-assembly is employed to prepare a series of CO3 based porous coordination polymers, viz. 1, [H2N(CH3)(2)](2)[CO3(ip)(4)]center dot H2O, 2, [H2N(CH3)(2)](2)[CO3(bdc)(4)]center dot(DMF)(2), 3, [H2N(CH3)(2)](2)[CO3(bpdc)(4)]center dot(CH3OH)(2)(DMF)1.5, where ip, bdc, bpdc, and DMF are 1,3-benzenedicarboxylate, 1,4-benzenedicarboxylate, 4,4'-biphenyldicarboxylate, and N,N'-dimethylformamide, respectively. Via different organic connectors such as ip, bdc, and bpdc, such CO3 molecular building blocks (MBB), [CO3(CO2)(8)](2-), are associated together to give a tunable 8-connected topological framework, viz. 4(24) 6(4) for 1, 3(6) 4(14) 5(7)6 for 2, and 3(6) 4(18) 5(3)6 for 3. Upon the geometry and the length of organic connectors, their corresponding porosity occupied by c counterions plus solvent molecules also can be tunable, for example, with the consideration of [H2N(CH3)(2)](+) counterions, the solvent-accessible volume is 460.2 angstrom(3) for 1, equal to 23.9% of the cell volume, 3320.4 angstrom(3) for 2, equal to 56.3% of the cell volume, 4107.2 angstrom(3) for 3, equal to 50% of the cell volume. Notably, besides these outstanding features of tunable 8-connected topology and porosity, their magnetic properties such as ferromagnetic behavior without magnetic ordering for 1, spin-canting and metamagnetic behavior with magnetic ordering for 2, as well as spin-canting, metamagnetic, and spin-glass behavior with magnetic ordering for 3 also can be tunable.