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Electronic Consequences of Ligand Substitution at Heterometal Centers in Polyoxovanadium Clusters: Controlling the Redox Properties through Heterometal Coordination Number
Author(s) -
Meyer Rachel L.,
Anjass Montaha H.,
Petel Brittney E.,
Brennessel William W.,
Streb Carsten,
Matson Ellen M.
Publication year - 2020
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.201905624
Subject(s) - redox , electrochemistry , chemistry , ligand (biochemistry) , cluster (spacecraft) , chloride , delocalized electron , ion , crystallography , electronic structure , inorganic chemistry , computational chemistry , electrode , organic chemistry , receptor , computer science , biochemistry , programming language
The rational control of the electrochemical properties of polyoxovanadate‐alkoxide clusters is dependent on understanding the influence of various synthetic modifications on the overall redox processes of these systems. In this work, the electronic consequences of ligand substitution at the heteroion in a heterometal‐functionalized cluster was examined. The redox properties of [V 5 O 6 (OCH 3 ) 12 FeCl] ( 1‐[V 5 FeCl] ) and [V 5 O 6 (OCH 3 ) 12 Fe]X ( 2‐[V 5 Fe]X ; X=ClO 4 , OTf) were compared in order to assess the effects of changing the coordination environment around the iron center on the electrochemical properties of the cluster. Coordination of a chloride anion to iron leads to an anodic shift in redox events. Theoretical modelling of the electronic structure of these heterometal‐functionalized clusters reveals that differences in the redox profiles of 1‐[V 5 FeCl] and 2‐[V 5 Fe]X arise from changes in the number of ligands surrounding the iron center (e.g., 6‐coordinate vs. 5‐coordinate). Specifically, binding of the chloride to the sixth coordination site appears to change the orbital interaction between the iron and the delocalized electronic structure of the mixed‐valent polyoxovanadate core. Tuning the heterometal coordination environment can therefore be used to modulate the redox properties of the whole cluster.