Premium
Trapping the δ Isomer of the Polyoxometalate‐Based Keggin Cluster with a Tripodal Ligand
Author(s) -
Sartzi Harikleia,
Miras Haralampos N.,
VilàNadal Laia,
Long DeLiang,
Cronin Leroy
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201505377
Subject(s) - polyoxometalate , keggin structure , chemistry , tungstate , single crystal , vanadium , crystallography , ligand (biochemistry) , cluster (spacecraft) , crystal structure , ion , photochemistry , catalysis , inorganic chemistry , organic chemistry , biochemistry , receptor , computer science , programming language
Abstract We report the synthesis, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ‐isomer of the Keggin polyoxometalate polyanion. A family of δ‐Keggin polyoxoanions of the general formula, (TEA)H p Na q [H 2 M 12 (XO 4 )O 33 (TEA)]⋅ r H 2 O where p , q , r =[2,3,8] for 1 and [4,1,4] for 2 were isolated by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster thereby stabilizing the polyanionic δ‐Keggin archetype. The δ‐Keggin species were characterized by single‐crystal X‐ray diffraction, FT‐IR, UV/Vis, NMR, and ESI‐MS spectrometry. Electronic structure and structure–stability correlations were evaluated by means of DFT calculations. The compounds exhibited multi‐electron transfer and reversible photochromic properties by undergoing single‐crystal‐to‐single‐crystal (SC–SC) transformations accompanied with color changes under light.