A Synthetic,Structural, Spectroscopic and DFT study of ReI,CuI, RuII and IrIII Complexes Containing Functionalised Dipyrido[3,2‐a:2′,3′‐c]phenazine (dppz)

The ligands 11‐cyanodipyrido[3,2‐a:2′,3′‐c]phenazine and 2‐(11‐dipyrido[3,2‐a:2′,3′‐c]phenazine)‐5‐phenyl‐1,3,4‐oxadiazole have been coordinated to Re^I, Cu^I, Ru^II and Ir^III metal centres. Single‐crystal X‐ray analyses were performed on fac‐chlorotricarbonyl(11‐cyanodipyrido[3,2‐a:2′,3′‐c]phenazine)rhenium (C₂₂H₉ClN₅O₃Re, a=6.509(5), b=12.403(5), c=13.907(5) Å, α=96.88(5), β=92.41(5), γ=92.13(5)°, triclinic, P , Z=2) and bis‐2,2′‐bipyridyl(2‐(11‐dipyrido[3,2‐a:2′,3′‐c]phenazine)‐5‐phenyl‐1,3,4‐oxadiazole)ruthenium triflate ? 2 CH₃CN (C₅₂H₃₆F₆N₁₂O₈RuS₂, a=10.601(5), b=12.420(5), c=20.066(5) Å, α=92.846(5), β=96.493(5), γ=103.720(5)°, triclinic, P , Z=2). The ground‐ and excited‐state properties of the ligands and complexes have been investigated with a range of techniques, including electrochemistry, absorption and emission spectroscopy, spectroelectrochemistry and excited‐state lifetime studies. Spectroscopic, time‐resolved and DFT studies reveal that the ligand‐centred (LC) transitions and their resultant excited states play an important role in the photophysical properties of the complexes. Evidence for the presence of lower‐lying metal‐to‐ligand charge‐transfer transitions is obtained from resonance Raman spectroscopy, but nanosecond transient Raman experiments suggest that once excited, the ³LC state is populated.