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New Perspectives for Old Clusters: Anderson–Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3 d–4 f Species
Author(s) -
Artetxe Beñat,
Reinoso Santiago,
San Felices Leire,
Lezama Luis,
GutiérrezZorrilla Juan M.,
Vicent Cristian,
Haso Fadi,
Liu Tianbo
Publication year - 2016
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.201504768
Subject(s) - polyoxometalate , cluster (spacecraft) , crystallography , chirality (physics) , tungstate , chemistry , derivative (finance) , series (stratigraphy) , ring (chemistry) , stereochemistry , inorganic chemistry , physics , chiral symmetry , catalysis , organic chemistry , paleontology , quantum mechanics , computer science , financial economics , nambu–jona lasinio model , economics , biology , programming language , quark
Abstract A series of nine [Sb 7 W 36 O 133 Ln 3 M 2 (OAc)(H 2 O) 8 ] 17− heterometallic anions ( Ln 3 M 2 ; Ln=La–Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs‐type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW 9 O 33 } capping unit formed by a planar {MW 6 O 24 } fragment to which three {WO 2 } groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ɛ‐Keggin cluster. It is shown, for the first time, that classical Anderson–Evans {MW 6 O 24 } anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk‐shaped species is also revealed. The Ln 3 M 2 anions possess chirality owing to a {Sb 4 O 4 } cluster being encapsulated in left‐ or right‐handed orientations. Their ability to self‐associate in blackberry‐type vesicles in solution has been assessed for the Ce 3 Co 2 derivative.