Characterization of three new divalent zinc coordination polymers involving fluorinated carboxylate tecton via the modulation of heterocyclic N-donor co-ligands

Abstract: Three new fluorous coordination polymers with a fluorinated carboxylate tecton and N-donor co-ligands, {[Zn2(hfipbb)2(phen)2]·2H2O} n (1), [Zn2(hfipbb)2(bipy)(H2O)] n (2), and [Zn5(hfipbb)4 (Hhfipbb)2 (bpp)] n (3), [H2hfipbb=4,4′-(hexafluoroisopropylidene)bis(benzoic acid), phen=1,10-phenthroline, bipy=4,4′-bipyridine, and bpp=1,3-bi(4-pyridyl)propane], have been prepared and characterized by elemental analysis, IR spectra, and X-ray diffraction. Compound 1 exhibits a 3D supramolecular network assembled from two independent 1D chain motifs [Zn(hfipbb)(phen)] through π⋯π stacking, and C–H⋯F and O–H⋯O interactions. Compound 2 features 2D undulating layer structure with 44-sql network. Whereas, in compound 3, pentanuclear [Zn5(η 2-O)2(μ 2-η 1:η 1-CO2)]2− cores are bridged by hfipbb2− and bpp ligands into a 3D 6-connected sxd framework with a point symbol of (33·46·55·6). The diverse arrangements of the compounds show the modulation of the heterocyclic N-donor co-ligands can suitably mediate the coordination requirement of metal centers as well as the binding modes of fluorinated carboxylate tecton, which consequently generate diverse crystalline architectures. In addition, the properties of thermogravimetric analysis, X-ray powder diffraction, and photoluminescent behaviors of the compounds have also been discussed. [Copyright &y& Elsevier]