Exploring Bonding Properties and Photophysical Behavior of Naphthoquinone-Based Rhenium(I) Tricarbonyl Complexes: A Combined Experimental and Theoretical Approach

Abstract

In this work, we describe the synthesis, characterization, and spectroscopic properties of four new rhenium(I) tricarbonyl complexes bearing a pyridyl imidazole-naphthoquinone (Py-Im-Nq) ligand. The spectroscopic, X-ray, and electrochemical analyses confirm the formation of neutral complexes in all cases. Although the Py-Im-Nq ligand possesses two distinct chelating fragments, we observed a selective formation of the N,N-isomer rather than the N,O-coordination. EDA calculations revealed that the origin of the N,N-linkage isomerism results from more favorable electrostatic interactions present in the N,N-coordination. Furthermore, EDA-NOCV analysis indicated that the bonding situation in these complexes can be described by the Dewar–Chatt–Duncanson model, providing a quantitative characterization of the donation and back-donation interaction components in these complexes. Finally, we examined the spectroscopic behavior (UV–vis and photoluminescence) of these new rhenium(I) complexes in solution. The characterization of the excited states was performed using TD-DFT and density difference isosurfaces. It was found that, in contrast to typical fac-[Re(NN)(CO)₃L]^0/+ systems, the low-lying transitions exhibit intraligand (IL) character, with charge transfer predominantly occurring from the imidazole ring to the carbonyl group in the quinone moiety. In contrast, a mixed metal-to-ligand charge transfer (MLCT)/IL transition is assigned to the electronic excitation at shorter wavelengths.