Near-infraredC-term MCD spectroscopy of octahedral uranium(v) complexes

Daniel J. Curran, Gaurab Ganguly, Yonaton N. Heit, Nikki J. Wolford, Stefan G. Minasian, Matthias W. Löble, Samantha K. Cary, Stosh A. Kozimor, Jochen Autschbach, Michael L. Neidig

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

C-term magnetic circular dichroism (MCD) spectroscopy is a powerful method for probing d-d and f-f transitions in paramagnetic metal complexes. However, this technique remains underdeveloped both experimentally and theoretically for studies of U(v) complexes ofOhsymmetry, which have been of longstanding interest for probing electronic structure, bonding, and covalency in 5f systems. In this study,C-term NIR MCD of the Laporte forbidden f-f transitions of [UCl6]and [UF6]are reported, demonstrating the significant fine structure resolution possible with this technique including for the low energy Γ7→ Γ8transitions in [UF6]. The experimental NIR MCD studies were further extended to [U(OC6F5)6], [U(CH2SiMe3)6], and [U(NC(tBu)(Ph))6]to evaluate the effects of ligand-type on the f-f MCD fine structure features. Theoretical calculations were conducted to determine the Laporte forbidden f-f transitions and their MCD intensity experimentally observed in the NIR spectra of the U(v) hexahalide complexes,viathe inclusion of vibronic coupling, to better understand the underlying spectral fine structure features for these complexes. These spectra and simulations provide an important platform for the application of MCD spectroscopy to this widely studied class of U(v) complexes and identify areas for continued theoretical development.

Original languageEnglish
Pages (from-to)5483-5492
Number of pages10
JournalDalton Transactions
Volume50
Issue number16
DOIs
StatePublished - Apr 28 2021
Externally publishedYes

Funding

M. L. N. acknowledges support for this work from the U.S. Department of Energy, Office of Science, Early Career Research Program under Award DE-SC0016002. J. A. acknowledges support from the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Heavy Element Chemistry, grant DE-SC0001136 for the theoretical component of this study. S. G. M. was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences Heavy Element Chemistry Program of the U.S. Department of Energy at LBNL under contract no. DE-AC02-05CH11231. S. A. K. acknowledges support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry program (2020LANLE372). LANL is an affirmative action/equal opportunity employer managed by Triad National Security, LLC, for the National Nuclear Security Administration of the U.S. DOE. We thank the Center for Computational Research (CCR) at the University of Buffalo for providing computational resources.

Fingerprint

Dive into the research topics of 'Near-infraredC-term MCD spectroscopy of octahedral uranium(v) complexes'. Together they form a unique fingerprint.

Cite this