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Abstract
Bent uranyl complexes can be formed with chloride ligands and 1,10-phenanthroline (phen) ligands bound to the equatorial and axial planes of the uranyl(VI) moiety, as revealed by the crystal structures, IR and Raman spectroscopy and quantum chemical calculations. With the goal of probing the influence of chloride and phenanthroline coordination enforcing the bending on the absorption and emission spectra of this complex, spin-orbit time-dependent density functional theory calculations for the bare uranyl complexes as well as for the free UO2Cl2 subunit and the UO2Cl2(phen)2 ligand were performed. The emission spectra has been fully simulated by ab initio methods and compared to experimental photoluminescence spectra, recorded for the first time for UO2Cl2(phen)2. Notably, the bending of uranyl in UO2Cl2 and UO2Cl2(phen)2 triggers excitations of the uranyl bending mode, yielding a denser luminescence spectrum.
Supplementary materials
Title
Supplementary data
Description
Justification for performing the calculations in the gas-phase. Table summarizing the QTAIM data, scalar relativistic transition energies, comparison of TDDFT and TDA transition energies for UO2Cl2 and TDDFT energies of UO2Cl2Ar2, TDDFT transition energies of UO2Cl2(phen)2 computed at with the SR-ZORA Hamiltonian in the gas phase and the COSMO water solvent. UO2Cl2, UO2Cl42- and UO2Cl2(phen)2 luminescence spectra assignment computed in the gas-phase at 4K.
The FT-IR and Raman spectra of UO2Cl2(phen)2 under 18O exchange
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