Year: 2025
Type: article
Abstract: The chemistry of pentavalent uranyl is of high interest due to the ion's central role as an intermediate in nuclear separations. However, due to the instability of [UO 2 ] + , little is known about its electronic structure. The synthesis and characterization of a pentavalent uranyl complex supported by a pyridine dipyrrolide pincer‐type ligand are reported. The pentavalent species is isolated following reduction of the hexavalent uranyl congener, allowing for direct comparisons to be made between the two species. The [UO 2 ] 2+ analog is nonemissive, but upon reduction, luminescence is “switched on” in the pentavalent uranyl complex, affording emission from a high‐energy state. Quantum chemical calculations support the experimental findings and help provide insight into the electronic structure of the excited states of the reduced complex. This work provides a unique example of ligand‐based non‐Kasha emission from a molecular pentavalent uranyl complex.
Source: ChemistryEurope
Authors: Leyla R. Valerio, Asmita Sen, William W. Brennessel, Carsten Milsmann, Jochen Autschbach, Ellen M. Matson
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: diamond
Awards: G363686360, COMPUTATIONAL STUDIES OF NMR CHEMICAL SHIFTS IN OPEN-SHELL ACTINIDE AND LANTHANIDE SYSTEMS, COMPUTATIONAL STUDIES OF NMR CHEMICAL SHIFTS IN OPEN-SHELL ACTINIDE AND LANTHANIDE SYSTEMS, G812591241, G8573626344, SPECTROSCOPIC AND SYNTHETIC STUDIES TO DEFINE ELECTRONIC STRUCTURE, BONDING AND REACTIVITY IN MOLECULAR ACTINIDE CHEMISTRY
OpenAlex ID: W7110861445