Topological diversity in copper aromatic meta-dicarboxylate coordination polymers with bis(pyridylformyl)piperazine coligands

摘要

Hydrothermal synthesis has afforded divalent copper coordination polymers containing bis(4-pyridylformyl)piperazine (4-bpfp) tethers and aromatic meta-dicarboxylate ligands. {[Cu(ip)(4-bpfp)]·2H_2O} _n (1, ip = isophthalate) possesses a (4, 4) rectangular grid structure with an unusual ABCD stacking pattern along a 4_1 screw axis. Sterically bulky substituents in the 5-position of the isophthalate ligands reduced the coordination polymer dimensionality, with [Cu _2(tBuip)_2(4-bpfp)(H_2O)_2] _n (2, tBuip = 5-tert-butylisophthalate) and {[Cu(MeOip)(HMeOip) _2(4-bpfp)]·3H_2O}_n (3, MeOip = 5-methoxyisophthalate) displaying 1D polymeric ladder and chain motifs, respectively. Compound 3 possesses a rare twofold interpenetrated binodal supramolecular hms net with (6~3)(6~98) topology. Longer meta-disposed acetate pendant arms induced a doubly interpenetrated 3D primitive cubic topology in {[Cu_2(1,3-phda)_2(H_2O) _2(4-bpfp)]}_n (4, 1,3-phda = 1,3-phenylenediacetate), which possesses antiferromagnetically coupled {Cu_2O_2} kernels (J = -6.14(8) cm~(-1)).