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Electronic Structure Studies on the Whole Keplerate Family: Predicting New Members
Author(s) -
Melgar Dolores,
Bandeira Nuno A. G.,
Bo Carles
Publication year - 2017
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.201605981
Subject(s) - bridging (networking) , ionic bonding , moiety , density functional theory , electronic structure , chemical stability , crystallography , nanoscopic scale , chemistry , oxide , context (archaeology) , materials science , chemical physics , stereochemistry , nanotechnology , computational chemistry , ion , organic chemistry , computer science , computer network , paleontology , biology
A comprehensive study of the electronic structure of nanoscale molecular oxide capsules of the type [{M VI (M VI ) 5 O 21 } 12 {M′ V 2 O 2 (μ‐X)(μ‐Y)(L n − )} 30 ] (12+ n )− is presented, where M,M′=Mo,W, and the bridging ligands X,Y=O,S, carried out by means of density functional theory. Discussion of the electronic structure of these derivatives is focused on the thermodynamic stability of each of the structures, the one having the highest HOMO‐LUMO gap being M=W, M′=Mo, X=Y=S. For the most well‐known structure M=M′=Mo, X=Y=O, [Mo 132 O 372 ] 12− , the chemical bonding of several ligands to the {Mo V 2 O 2 (μ‐O) 2 } linker moiety produces negligible effects on its stability, which is evidence of a strong ionic component in these bonds. The existence of a hitherto unknown species, namely W 132 with both bridging alternatives, is discussed and put into context.