The combined action of ultraviolet irradiation and microwave heating onto acetonitrile solution of [Re((Formula presented.))(CO) ₃(NCMe)]OTf ((Formula presented.) =phenantroline and neocuproine) afforded cis,trans-Re((Formula presented.))(CO) ₂(NCMe) ₂] ⁺ acetonitrile derivatives. Substitution of relatively labile NCMe with a series of aromatic N-donor ligands (pyridine, pyrazine, 4,4’-bipyridine, N-methyl-4,4’-bipyridine) gave a novel family of the diimine cis,trans-[Re((Formula presented.))(CO) ₂(L) ₂] ⁺ complexes. Photophysical studies of the obtained compounds in solution revealed unusually high absorption across the visible region and NIR phosphorescence with emission band maxima ranging from 711 to 805 nm. The nature of emissive excited states was studied using DFT calculations to show dominant contribution of ³MLCT (dπ(Re)→π*((Formula presented.))) character. Electrochemical (CV and DPV) studies of the monocationic diimine complexes revealed one reduction and one oxidation wave assigned to reduction of the diimine moiety and oxidation of the rhenium center, respectively.