UV-Vis Absorption Spectroscopy of Polonium(IV) Chloride Complexes: An Electronic Structure Theory Study.

More than a hundred years after its discovery, the chemistry of the polonium radioelement is still largely unknown. However, it is quite clear that the properties of this heavy element ( Z = 84) may be affected by relativistic effects, in particular scalar relativistic effects and the so-called spin-orbit coupling (SOC). In this Article, we revisit the interpretation of UV-vis absorption spectra of polonium(IV) complexes in HCl medium, reported decades ago. From the data, two complexes were hypothesized, complex I with a maximum of absorption at 344 nm (at low HCl concentration) and complex II with a maximum at 418 nm (the only visible peak for HCl concentrations above 0.5 M). By monitoring the absorbance at 344 and 418 nm as a function of both the HCl concentration and the pH, complex I was formulated as [Po(OH)Cl x]3- x while complex II was formulated as [PoCl2+ x]2- x. In this work, we study the ground-state geometries of the [Po(OH)Cl x]3- x and [PoCl2+ x]2- x complexes for x = 4-2, i.e. for the most probable complexes, with density functional theory (DFT), demonstrating that solvation can remarkably change the geometries of such systems. The electronic excitation energies are then computed with time-dependent DFT (TD-DFT), second-order N-electron valence state perturbation theory (NEVPT2), and contracted spin-orbit configuration interaction (c-SOCI), showing (i) that the SOC must be at play to obtain excitation energies in the right energy domain and (ii) that the quantum chemical calculations point toward x = 4, i.e., toward the [Po(OH)Cl4]- and [PoCl6]2- complexes.

Luminescent Dinuclear Copper(I) Complexes as Potential Thermally Activated Delayed Fluorescence (TADF) Emitters: A Theoretical Study.

The excited state properties of a series of binuclear NHetPHOS-Cu(I) complexes (NHetPHOS) have been investigated by means of density functional theory (DFT) and time-dependent DFT (TD-DFT). It is shown that experimental trends observed in powder, generally explored via S1 and T1 excited state energetics and S1 ⇔ T1 intersystem crossing (ISC) efficiency, are hardly analyzed on the basis of excited state properties calculated in solution. Indeed, several local minima corresponding to various structural deformations are evident on the lowest excited state potential energy surfaces (PES) when solvent correction is applied, leading to a four-state thermally activated delayed fluorescence (TADF) mechanism. In contrast, preliminary simulations performed in the solid point to the reduction of nuclear flexibility and consequently to a rather simple two-state model.