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Supramolecular Structures of Titanium( IV )‐Substituted Wells–Dawson Polyoxotungstates
Author(s) -
Kortz Ulrich,
Hamzeh Shadia S.,
Nasser Niveen A.
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200204677
Subject(s) - crystallography , supramolecular chemistry , titanium , chemistry , crystal structure , stereochemistry , infrared spectroscopy , organic chemistry
Abstract The novel, dimeric titanium( IV )‐substituted phosphotungstate [(TiP 2 W 15 O 55 OH) 2 ] 14− ( 1 ) has been synthesized and characterized by IR and 31 P NMR spectroscopy, elemental analysis, and single‐crystal Xray diffraction. The polyanion consists of two [P 2 W 15 O 56 ] 12− Wells–Dawson moieties linked through two titanium( IV ) centers. Polyanion 1 is a dilacunary species and represents the first Ti‐containing sandwich‐type structure. The titanium centers are octahedrally coordinated by three oxygen atoms of each P 2 W 15 O 56 subunit. The edge‐shared TiO 6 units are symmetrically equivalent and have no terminal ligands. Polyanion 1 shows a chiral distortion within each P 2 W 15 Ti fragment. We also report on the structural characterization of the tetrameric, supramolecular species [{Ti 3 P 2 W 15 O 57.5 (OH) 3 } 4 ] 24− ( 2 ). Polyanion 2 is composed of four equivalent P 2 W 15 Ti 3 fragments, fused together through terminal TiO bonds, leading to a structure with T d symmetry.