Insight into the Structural and Emissive Behavior of a Three-Dimensional Americium(III) Formate Coordination Polymer

Author(s)

Nicholas, Aaron D. ; Arteaga, Ana ; Ducati, Lucas C. ; Buck, Edgar C. ; Autschbach, Jochen ; Surbella III, Robert G.

• Document type: Journal article
• Source: CHEMISTRY-A EUROPEAN JOURNAL; v. N/A, p. 11-pg., 2023-06-13.

Abstract

We report the structural, vibrational, and optical properties of americium formate (Am(CHO2)(3)) crystals synthesized via the in situ hydrolysis of dimethylformamide (DMF). The coordination polymer features Am3+ ions linked by formate ligands into a three-dimensional network that is isomorphous to several lanthanide analogs, (e. g., Eu3+, Nd3+, Tb3+). Structure determination revealed a nine-coordinate Am3+ metal center that features a unique local C-3v symmetry. The metal-ligand bonding interactions were investigated by vibrational spectroscopy, natural localized molecular orbital calculations, and the quantum theory of atoms in molecules. The results paint a predominantly ionic bond picture and suggest the metal-oxygen bonds increase in strength from Nd-O<Eu-O<Am-O. The optical properties were probed using diffuse reflectance and photoluminescence spectroscopies. Notably, the rarely reported D-5(1 ')-> F-7(0 ') emission band is observed and dominates the emission spectrum. This behavior is unusual and is attributed to the C-3v coordination environment of the metal center. (AU)

• FAPESP's process: 17/17750-3 - Solvent Effect in NMR Parameters by ab initio Molecular Dynamics
• Grantee: Lucas Colucci Ducati
• Support Opportunities: Regular Research Grants