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pH‐Specific Halide‐Dependent Materials from Zr IV /Hydroxycarboxylic Acid/Aromatic Chelator Reactivity: Architecture–Lattice Dimensionality and Spectroscopic Fingerprint Relations
Author(s) -
Halevas Eleftherios,
Karamelidou Asimenia,
Hatzidimitriou Antonios,
Mateescu Constantin,
Salifoglou Athanasios
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402864
Subject(s) - chemistry , chelation , reactivity (psychology) , crystallography , ternary operation , nuclear magnetic resonance spectroscopy , reagent , inorganic chemistry , stereochemistry , medicine , alternative medicine , pathology , computer science , programming language
The chemical reactivity of binary and ternary Zr 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 2 F 6 (C 6 H 4 O 7 ) 2 ](CH 6 N 3 ) 6 · H 2 O ( 1 ), [Zr 2 F 6 (C 4 H 3 O 5 ) 2 ](NH 4 ) 4 · 3H 2 O ( 2 ), [Zr 2 (C 4 H 3 O 5 ) 2 (C 4 H 4 O 5 ) 2 (C 4 H 5 O 5 ) 2 ](CH 6 N 3 ) 4 · 4.5H 2 O ( 3 ), and [Zr 2 (C 4 H 3 O 5 ) 2 (C 4 H 4 O 5 ) 2 (C 4 H 5 O 5 ) 2 ](C 12 H 8 N 2 )(C 12 H 9 N 2 ) 2 (CH 6 N 3 ) 2 · 6H 2 O ( 4 ). Compounds 1 – 4 were characterized by elemental analysis, FTIR spectroscopy, TGA, 13 C‐CPMAS, 19 F‐DPMAS, and 1 H CRAMPS NMR spectroscopy, and X‐ray crystallography. The structures of 1 – 4 reveal the influence of fluoride in the starting Zr IV reagents on the identity of the Zr 2 O 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 IV materials with defined physicochemical properties can arise at the binary and ternary level.