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 ZnII-hfipbb binary system (H2hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid)). The solvothermal reaction of zinc acetate and H2hfipbb with the different stoichiometries of dps from 0.1 to 0.4 mmol has resulted in three new coordination polymers, [Zn(hfipbb)(H2hfipbb)0.5]n (1) and [Zn2(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 (7·82)(4·7·9)(72·84)(4·72·8·92) net and 2-fold interpenetrating (83)2(85·10) net. In addition, the properties of thermogravimetric analysis, X-ray powder diffraction, and photoluminescent behaviors of the complexes have been also discussed.