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The chelate ligands 1 l-R-dipyrido[3,2-a:2',3'~]phenazine, dppz-R (R = NHz, CH3, H, COOH, NOz) and the Re(dppz-R)(CO)&l (R = NHz, COOH, NO2) complexes were synthesized and characterized by conventional techniques. The influence of the donor and acceptor properties of the R substituents on the ligand properties were studied by spectroscopic techniques such as 'H-NMR and UV-Vis. Theoretical calculations were also achieved, mainly to interpret and understand the experimental spectra.

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A series of tricarbonyl rhenium(I) complexes of the type fac‐[ReI(CO)3(ppl)(L)]0/+, where ppl is pyrazino[2,3‐f][1,10]phenanthroline, and where L is Cl−, TfO−, 4‐(tert‐butyl)pyridine (tBu‐py), 4‐methoxypyridine (MeO‐py), 4,4′‐bipyridyl (bpy), or 10‐(picolin‐4‐yl)phenothiazine (pptz), were synthesized and fully characterized. In all complexes, an increment in the electron‐acceptor properties of ppl compared to the free ligand was observed. This effect was more significant for pyridine‐type ligands, especially for pptz, compared to Cl− or TfO−. The properties of fac‐[Re(CO)3(ppl)(pptz)]PF6 were compared with those of the analogous compound fac‐[Re(CO)3(dppz)(pptz)]PF6, where dppz is dipyrido(3,2‐a : 2′,3′‐c)phenazine, the goal being to generate long‐lived excited charge‐transfer (CT) states. In this respect, fac‐[Re(CO)3(ppl)(pptz)]PF6 seems to be a promising candidate.