Chemistry & Biochemistry Seminar: "A nucleation journey with polyoxovanadate-alkoxide clusters"

By: Dr. Pere Miro - University of South Dakota

Abstract

Polyoxovanadate-alkoxide clusters are a class of electroactive species with redox properties that can be tuned during their synthesis. However, their nucleation mechanism and structure-redox relationships remain largely unknown, thus limiting the rational design of new species with specific redox properties. Here, we present our research group's journey in the computational exploration of the nucleation pathways and redox properties of various polyoxovanadate-alkoxide hexameric species such as [(V^V_6-nV^IV_nO₆)(O)(O-CH₃)₁₂]_n, transition metal functionalized [(V^V_5-nV^IV_nO₅)(O-CH₃)₁₂(O)(M-Cl)]^m (with M=Fe, Co, Ti, Zr, or Hf), and cyclic [(V^IV₆O₆)(O-R)₁₂] with R=-CH₃, -CH₂-CH₃, -(CH₂)₂-CH₃, and -CH(CH₃)₂ species. Modern density functional theory methodologies were used to study the nucleation intermediates and evaluate the redox potentials of polyoxovanadate-alkoxide species. Furthermore, we benchmarked our density functional theory calculations against domain-based local pair natural orbital coupled cluster calculations, DLPNO-CCSD(T). We validated the applicability of this methodology to polyoxovanadate-alkoxides. These studies will bring us closer to understanding the structure-redox relationships of POV-alkoxides and identifying new synthetic targets with improved redox properties.

Free