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Electronic Structure of Monodithiolated IronOxotungsten Heterometallic Complexes: Integer‐Spin FeW Assembly
Author(s) -
Bose Moumita,
Moula Golam,
Sarkar Sabyasachi
Publication year - 2013
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201300245
Subject(s) - electron paramagnetic resonance , crystallography , chemistry , antiferromagnetism , magnetism , moiety , ground state , mössbauer spectroscopy , electronic structure , stereochemistry , nuclear magnetic resonance , computational chemistry , physics , atomic physics , condensed matter physics
FeW heterometallic complexes, in which an FeX 2 (X=Cl, SPh) moiety is attached to monodithiolene oxotungsten through a sulfide bridge, that is, [Ph 4 P] 2 [Cl 2 Fe(S) 2 WOS 2 ] ( 1 ), [Ph 4 P] 2 [Cl 2 Fe(S) 2 WOS 2 (DMED)] ( 2 , DMED=dimethylethylenedicarboxylate), [Ph 4 P] 2 [Cl 2 Fe(S) 2 WO(tdt)] ( 3 , tdt=toluenedithiolate), [Ph 4 P] 2 [(SPh) 2 Fe(S) 2 WO(tdt)] ( 4 ), and [Ph 4 P] 2 [Cl 2 Fe(S) 2 WO(edt)] ( 5 , edt=ethanedithiolate), are reported. Mössbauer and EPR spectroscopy, magnetism, electrochemistry, and electronic structural analysis based on DFT and TD‐DFT calculations show the transfer of electron from the iron center to the tungsten center, thus resulting in a ferromagnetically coupled Fe III W V unit, along with antiferromagnetic intermolecular interactions, from the starting Fe II and W VI compounds. A net spin of a S =3 ground state, which arises from ferromagnetically coupled Fe III and W V atoms, displays a rare X‐band EPR in normal mode at g ≈7 in the solid state.