Stoichiometry of N-Donor Ligand Mediated Assembly in the Zn^II-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 (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.