2-Azabutadiene complexes of rhenium(I): S,N-chelated species with photophysical properties heavily governed by the ligand hidden traits

The reaction of [Re(CO)3(THF)(μ-Br)]2 or [Re(CO)5X] (X = Cl, Br, I) with the diaryl-2-azabutadienes [(RS)2C[double bond, length as m-dash]C(H)-N[double bond, length as m-dash]CAr2] containing two thioether arms at the 4,4-position forms the luminescent S,N-chelate complexes fac-[(OC)3ReX(RS)2C[double bond, length as m-dash]C(H)-N[double bond, length as m-dash]CAr2] (1a-h). The halide abstraction by silver triflate converts [(OC)3ReCl(PhS)2C[double bond, length as m-dash]C(H)-N[double bond, length as m-dash]CPh2] (1c) to [(OC)3Re(OS([double bond, length as m-dash]O)2CF3)(PhS)2C[double bond, length as m-dash]C(H)-N[double bond, length as m-dash]CPh2] (1j) bearing a covalently bound triflate ligand. The cyclic voltammograms reveal reversible S^N ligand-centred reduction and irreversible oxidation waves for all complexes. The crystal structures of nine octahedral complexes have been determined along with that of (NaphtylS)2C[double bond, length as m-dash]C(H)-N[double bond, length as m-dash]CPh2 (L6). A rich system of weak non-covalent intermolecular secondary interactions through CHX(Cl, Br)Re, CHO, COπ(Ph), CHπCO, CHO and CHS contacts has been evidenced. The photophysical properties have been investigated by steady-state and time-resolved absorption (fs transient absorption, fs-TAS) and emission (ns-TCSPC and ps-Streak camera) spectroscopy in 2-MeTHF solution at 298 and 77 K. The emission bands are composed of either singlet (450 < λmax < 535 nm) and/or triplet emissions (at 77 K only, λmax < 640 nm, or appearing as a tail at λ > 600 nm), which decay in a multiexponential manner for the fluorescence (short ps (i.e.