pH-Specific Halide-Dependent Materials from ZrIV/Hydroxycarboxylic Acid/Aromatic Chelator Reactivity: Architecture-Lattice Dimensionality and Spectroscopic Fingerprint Relations

• Published in: European journal of inorganic chemistry Vol. 2015; no. 4; pp. 664 - 679
• Main Authors: Halevas, Eleftherios, Karamelidou, Asimenia, Hatzidimitriou, Antonios, Mateescu, Constantin, Salifoglou, Athanasios
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01-02-2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: Hydroxycarboxylic acids; Materials science; Spectroscopic fingerprints; Structural correlations; Zirconium
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201402864

The chemical reactivity of binary and ternary ZrIV/hydroxycarboxylic acid/(N,N‐aromatic chelator) systems (hydroxycarboxylic acid = citric, malic acid; N,N‐aromatic chelator = 1,10‐phenanthroline) has been investigated in a pH‐specific manner, giving rise to the new binary and ternary crystalline materials [Zr2F6(C6H4O7)2](CH6N3)6·H2O (1), [Zr2F6(C4H3O5)2](NH4)4·3H2O (2), [Zr2(C4H3O5)2(C4H4O5)2(C4H5O5)2](CH6N3)4·4.5H2O (3), and [Zr2(C4H3O5)2(C4H4O5)2(C4H5O5)2](C12H8N2)(C12H9N2)2(CH6N3)2·6H2O (4). Compounds 1–4 were characterized by elemental analysis, FTIR spectroscopy, TGA, 13C‐CPMAS, 19F‐DPMAS, and 1H CRAMPS NMR spectroscopy, and X‐ray crystallography. The structures of 1–4 reveal the influence of fluoride in the starting ZrIV reagents on the identity of the Zr2O2‐containing dinuclear assemblies in the arisen 3D architectures. The uniquely defined spectroscopic data, including the NMR data, corroborate the X‐ray structures of 1–4 and reflect the contribution of the intra/intermolecular interactions to the structural speciation of the investigated systems. Collectively, the work 1) depicts the factors that determine the nature and properties of the emerging synthetic materials in the investigated systems, 2) formulates structural architecture–lattice dimensionality and spectroscopic fingerprint correlations, and 3) projects the framework through which new ZrIV materials with defined physicochemical properties can arise at the binary and ternary level.
The pH‐specific reactivity of binary/ternary ZrIV/citric (malic) acid/(phenanthroline) systems leads to inorganic/organic hybrid Zr2O2‐containing dinuclear assemblies with distinct 3D architectures. Structural speciation reveals the influence of halide on the ultimate structure and well‐defined factor correlations earmarking spectroscopic identity in the design of advanced materials.