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The rational control of the electrochemical properties of polyoxovandate-alkoxide clusters is dependent on understanding the influence of various synthetic modifications on the overall redox processes of these systems. In this work, we examine the electronic consequences of ligand substitution at the heteroion in a heterometal-functionalized cluster. 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). Binding of the chloride to the sixth coordination site changes the orbital interaction between the iron and the delocalized electronic structure of the mixed-valent polyoxovanadate core. Tuning of the heterometal coordination environment can therefore be used to modulate the redox properties of the whole cluster.
This article was published in the following journal.
Name: Chemistry (Weinheim an der Bergstrasse, Germany)
A new biologically relevant cubane-type artificial inorganic ligand was developed to support 3d-transition metal ions of Mn(II), Co(II), Ni(II), Zn(II), Fe(III), and also In(III). All of the reactions...
The electronic structure and the photochemistry of copper formate clusters Cu(I)2(HCO2)3- and Cu(II)n(HCO2)2n+1-, n ≤ 8, are investigated in the gas phase using UV/Vis spectroscopy in combination ...
We report the synthesis, characterization, and reactivity of [LFeO(ArIm)Fe][OTf], the first Hammett series of a site-differentiated cluster. The cluster reduction potentials and CO stretching frequenc...
The elucidation of magnetostructural correlations between bridging ligand substitution and strength of magnetic coupling is essential to the development of high-temperature molecule-based magnetic mat...
Seeking novel superatoms with tunable electronic and magnetic properties has attracted much interest due to their potential application in cluster assembly nanomaterials. By employing density function...
The aim of the study is to examine whether electronic compliance monitoring in real time could offer some advantages compared to normal electronic monitoring in opioid substitution treatme...
Electronic dispensers for polypharmacy are used in home care to assist patients with their medication management and to improve adherence. Opioid dependent patients with substitution thera...
Patients with chronic hepatitis C that are under opiate substitution therapy are likely to have psychiatric comorbidities such as depression; hence an Interferon based therapy is contraind...
Early Maladaptive Schemas (EMS) are overactivated in euthymic bipolar disorders (BD) and are associated with poor psychosocial functioning and higher suicidality. The first objective of t...
The purpose of this study is to confirm anticipated substitution dose of the vitamin D for sustained blood level during winter time in patients with inflammatory bowel diseases (IBD)
The consequences of exposing the FETUS in utero to certain factors, such as NUTRITION PHYSIOLOGICAL PHENOMENA; PHYSIOLOGICAL STRESS; DRUGS; RADIATION; and other physical or chemical factors. These consequences are observed later in the offspring after BIRTH.
The naturally occurring or experimentally induced replacement of one or more AMINO ACIDS in a protein with another. If a functionally equivalent amino acid is substituted, the protein may retain wild-type activity. Substitution may also diminish, enhance, or eliminate protein function. Experimentally induced substitution is often used to study enzyme activities and binding site properties.
Electronic implements worn on the body as an implant or as an accessory. Examples include wearable diagnostic devices, wearable ACTIVITY TRACKERS, wearable INFUSION PUMPS, wearable computing devices, SENSORY AIDS, and electronic pest repellents.
Education centers authorized by the Comprehensive Health Manpower Training Act, 1971, for the training of health personnel in areas where health needs are the greatest. May be used for centers other than those established by the United States act.
Electronic devices that increase the magnitude of a signal's power level or current.