pH-Specific Halide-Dependent Materials from Zr super(IV)/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: 01-02-2015
• Subjects: Architecture; Binary systems; Chelating; Correlation; Fingerprints; Speciation; Spectroscopy; Three dimensional
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201402864

The chemical reactivity of binary and ternary Zr super(IV)/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 [Zr sub(2)F sub(6)(C sub(6)H sub(4)O sub(7)) sub(2)](CH sub(6)N sub(3)) sub(6).H sub(2) O (1), [Zr sub(2)F sub(6)(C sub(4)H sub(3)O sub(5)) sub(2)](NH sub(4)) sub(4).3H sub(2)O (2), [Zr sub(2)(C sub(4)H sub(3)O sub(5)) sub(2)(C sub(4)H sub(4)O sub(5)) sub(2)(C sub(4)H sub(5) sub(5)) sub(2)](CH sub(6)N sub(3)) sub(4).4.5H sub(2)O (3), and [Zr sub(2)(C sub(4)H sub(3)O sub(5)) sub(2)(C sub(4)H sub(4)O sub(5)) sub(2)(C sub(4)H sub(5) sub(5)) sub(2)](C sub(12)H sub(8)N sub(2))(C sub(12)H sub(9)N sub(2)) sub(2)(CH sub(6) sub(3)) sub(2).6H sub(2)O (4). Compounds 1-4 were characterized by elemental analysis, FTIR spectroscopy, TGA, super(13)C-CPMAS, super(19)F-DPMAS, and super(1)H CRAMPS NMR spectroscopy, and X-ray crystallography. The structures of 1-4 reveal the influence of fluoride in the starting Zr super(IV) reagents on the identity of the Zr sub(2)O sub(2)-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 Zr super(IV) materials with defined physicochemical properties can arise at the binary and ternary level. The pH-specific reactivity of binary/ternary Zr super(IV)/citric (malic) acid/(phenanthroline) systems leads to inorganic/organic hybrid Zr sub(2)O sub(2)-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.