Solvent Effect on NMR Parameters of Tl(III) and Pt(IV) Complexes by ab initio Molecular Dynamics and Relativistic Calculations

• Grant number: 24/17236-1
• Support Opportunities: Regular Research Grants
• Start date: February 01, 2025
• End date: January 31, 2028
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Lucas Colucci Ducati
• Grantee: Lucas Colucci Ducati
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Associated researchers: Luciano Nassif Vidal

Abstract

The influence of solvent coordination on the shielding tensor /chemical shift and on the indirect spin-spin coupling constants of the mononuclear complexes of Tl(III) and Pt(IV) will be the target of this study. These salts are in equilibrium in an aqueous medium and/or high acid concentration, requiring the use of explicit solvation and a description of the solute-solvent system dynamically. The estimated theoretical values ¿¿of the parameters magnetics with static geometries at DFT level, with inclusion of implicit solvent effect and Hamiltonian with relativistic correction, deviate from the experimental values ¿¿by about 30% or more depending on the case. To improve the description of the solute-solvent system and the influence of the solvent on the spectroscopic parameters, the Kohn-Sham (KS) Car-Parrinello (CPMD) and hybrid KS calculations of magnetic properties will be used. That state-of-the-art computational methodology, combining KS-CPMD and hybrid KS-DFT calculations todetermination of magnetic properties, has been successfully applied to metal compounds ofdinuclear transitions Tl Pt and Pt Pt and 199 Hg adducts, enabling structural elucidation in theequilibrium and the fundamental role of the solvent in the existence of these complexes in solution. (AU)