Push–pull effect – how to effectively control photoinduced intramolecular charge transfer processes in rhenium(i) chromophores with ligands of D–A or D–π–A structure†

Over the last five decades, diimine rhenium(I) tricarbonyl complexes have been extensively investigated due to their remarkable and widely tuned photophysical properties. These systems are regarded as attractive targets for design functional luminescent materials and performing fundamental studies of photoinduced processes in transition metal complexes. This review summarizes the latest developments concerning Re(I) tricarbonyl complexes bearing donor–acceptor (D–A) and donor–π–acceptor (D–π–A) ligands. Such compounds can be treated as bichromophoric systems with two close-lying excited states, metal-to-ligand charge transfer (MLCT) and intraligand-charge-transfer (ILCT). A role of ILCT transitions in controlling photobehaviour was discussed for Re(I) tricarbonyls with six different diimine cores decorated by various electron-rich amine, sulphur-based and π-conjugated aryl groups. It was evidenced that this approach is an effective tool for enhancement of the visible absorptivity, bathochromic emission shift and significant prolongation of the excited-state, opening up new possibilities in the development of more efficient materials and expand the range of their applications.