Electroswitchable Photoluminescence Activity: Synthesis, Spectroscopy, Electrochemistry, Photophysics, and X-ray Crystal and Electronic Structures of [Re(bpy)(CO)₃(C⋮CC₆H₄C⋮C)Fe(C₅Me₅)(dppe)][PF₆]<i>_n</i> (<i>n</i> = 0, 1)

A novel heterobimetallic alkynyl-bridged complex, [Re(bpy)(CO)3(C⋮CC6H4C⋮C)Fe(C5Me5)(dppe)], 1, and its oxidized species, [Re(bpy)(CO)3(C⋮CC6H4C⋮C)Fe(C5Me5)(dppe)][PF6], 2, have been synthesized and their X-ray crystal structures determined. A related vinylidene complex, [Re(bpy)(CO)3(C⋮CC6H4(H)CC)Fe(C5Me5)(dppe)][PF6], 3, has also been synthesized and characterized. The cyclic voltammogram of 1 shows a quasireversible reduction couple at −1.49 V (vs SCE), a fully reversible oxidation at −0.19 V, and a quasireversible oxidation at +0.88 V. In accord with the electrochemical results, density-functional theory calculations on the hydrogen-substituted model complex Re(bpy)(CO)3(C⋮CC6H4C⋮C)Fe(C5H5)(dHpe) (Cp = C5H5, dHpe = H2P(CH2)2PH2) (1-H) show that the LUMO is mainly bipyridine ligand π* in character while the HOMO is largely iron(II) d orbital in character. The electronic absorption spectrum of 1 shows low-energy absorption at 390 nm with a 420 nm shoulder in CH2Cl2, while that of 2 exhibits less intense low-energy bands at 432 and 474 nm and additional low-energy bands in the NIR at ca. 830, 1389, and 1773 nm. Unlike the related luminescent rhenium(I)−alkynyl complex [Re(bpy)(CO)3(C⋮CC6H4C⋮CH)], 4, complex 1 is found to be nonemissive, and such a phenomenon is attributed to an intramolecular quenching of the emissive dπ(Re) → π*(bpy) 3MLCT state by the low-lying MLCT and LF excited states of the iron moiety. Interestingly, switching on of the luminescence property derived from the dπ(Re) → π*(bpy) 3MLCT state can be demonstrated in the oxidized species 2 and the related vinylidene analogue 3 due to the absence of the quenching pathway.