Synthesis and Characterization of Luminescent Rhenium(I)−Platinum(II) Polypyridine Bichromophoric Alkynyl-Bridged Molecular Rods

The first class of luminescent heterobimetallic rhenium(I)−platinum(II) polypyridine alkynyl complexes, [(N ∧ N)(CO) 3 Re{C⋮C−(C 6 H 4 ) n −C⋮C}Pt(N ∧ N ∧ N)]OTf (N ∧ N = bpy, t Bu 2 bpy, (CF 3 ) 2 bpy, NO 2 phen; N ∧ N ∧ N = tpy, t Bu 3 tpy; n = 0, 1), has been successfully synthesized. The X-ray crystal structures of [(bpy)(CO) 3 Re{C⋮C−C 6 H 4 −C⋮C}Pt( t Bu 3 tpy)]OTf ( 1 ) and [(NO 2 phen)(CO) 3 Re{C⋮C−C 6 H 4 −C⋮C}Pt( t Bu 3 tpy)]OTf ( 4 ) have been determined. Their photophysical and electrochemical behavior have also been studied and discussed. An unexpected localization of the lowest-energy emissive state on the platinum(II) terpyridyl moiety in these heterometallic bichromophoric systems was observed.