Related Experiment Video
Updated: Jul 10, 2025
Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Modulation of the Band Gap and Redox Properties by Mixed Addenda in Sandwich Polyoxometalates
Ganga Singh1, Debaprasad Mandal1
1Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar 140001, Punjab, India.
Abstract:
Due to the wide range of applications of band-gap engineering in optoelectronics and photocatalysis, the rational design of polyoxometalate (POM) frameworks is highly desired. Here, we have successfully synthesized a series of mixed addenda (Mo and W) sandwich POMs by systematically varying pH, concentrations of salts, and counterions in Weakley-type sandwich POMs by incorporating Mo into the framework of tetrasubstituted sandwich POMs. Crystallographic analysis reveals the centrosymmetric structure; with variation in the Mo to W ratio, Mo preferentially binds to μ2 oxygen connected to transition metals in the sandwich position. UV-visible spectroscopy, electrochemical, and theoretical modeling rationalize the band-gap modulations. Theoretical studies and cyclic voltammograms indicate that during the reduction, the incoming electrons preferentially go to substituted transition metals followed by Mo. Flat band potential calculated from the Mott-Schottky enables tuning of the electronic properties of composites based on these sandwich POMs. Moreover, the dioxygen binding and activation studies of these polyoxometalates have been highlighted.
More Related Videos
05:47Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
04:51Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Related Concept Videos
02:51Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
02:42Valence Bond Theory
01:19Complexation Equilibria: The Chelate Effect
00:43Complexometric Titration: Ligands
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...