Stoichiometry of N-Donor Ligand Mediated Assembly in the ZnII-Hfipbb System: From a 2-Fold Interpenetrating Pillared-Network to Unique (3,4)-Connected Isomeric Nets

In this contribution, we devote our effort to explore the effect of stoichiometry of the 4,4'-dipyridylsulfide (dps) ligand on the final structures in the Zn-II-hfipbb binary system (H(2)hfipbb = 4,4'-(hexafluoroisopropylidene)bis(benzoic acid)). The solvothermal reaction of zinc acetate and H(2)hfipbb with the different stoichiometries of dps from 0.1 to 0.4 mmol has resulted in three new coordination polymers, [Zn(hfipbb)(H(2)hfipbb)(0.5)](n) (1) and [Zn-2(hfipbb)(2)(dps)(H2O)](n) (2a and 2b). The structure determination reveals that complex 1 displays a three-dimensional (3D) 2-fold parallel interpenetrating pillared-layer network with one-dimensional double left- and right-handed helical tubes. Complexes 2a and 2b are framework-isomeric as two unusual (3,4)-connected 3D coordination networks, i.e., a 4-nodal (7.8(2))(4.7.9)-(7(2).8(4))(4.7(2).8.9(2)) net and 2-fold interpenetrating (8(3))(2)(8(5).10) net. In addition, the properties of thermogravimetric analysis, X-ray powder diffraction, and photoluminescent behaviors of the complexes have been also discussed.