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

Abstract

The first class of luminescent heterobimetallic rhenium(I)−platinum(II) polypyridine alkynyl complexes, [(N∧N)(CO)3Re{C⋮C−(C6H4) n −C⋮C}Pt(N∧N∧N)]OTf (N∧N = bpy, t Bu2bpy, (CF3)2bpy, NO2phen; N∧N∧N = tpy, t Bu3tpy; n = 0, 1), has been successfully synthesized. The X-ray crystal structures of [(bpy)(CO)3Re{C⋮C−C6H4−C⋮C}Pt( t Bu3tpy)]OTf (1) and [(NO2phen)(CO)3Re{C⋮C−C6H4−C⋮C}Pt( t Bu3tpy)]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.

Electrochemistry and blocking properties of thin films of platinum phenylethynyl complexes

“…The significance of this result lies in the fact that while optical properties of PtPE thin films may arise from the HOMO, the LUMO, and their interaction, electrochemical oxidation in thin films accesses the Pt(II) center, not the HOMO. This has been observed in other Pt(II) compounds with alkynyl ligands [18,19].…”

Syntheses, characterization and sensitized lanthanide luminescence of heteronuclear Pt–Ln (Ln=Eu, Nd, Yb) complexes with 2,2′-bipyridyl ethynyl ligands

“…The Pt-C"C-C array is quasi-linear with Pt-C28-C29 = 179.0(1)°a nd C28-C29-C30 = 176.7(1)°. The Pt-N (1.952(8)-2.036(9) Å) and Pt-C (1.975(10) Å) distances are comparable to those in other platinum(II) terpyridyl acetylide analogues [18,24,25,34]. The 2,2 0 -bipyridyl rings in the C"CbpyC"C form a dihedral angle of 12.9°w…”

“…p * (Bu t 3 tpy) MLCT transition, mixed probably with some character from p(C"Cbpy/C"CbpyC "C) ? p * (Bu t 3 tpy) LLCT states [19,20,24,25,34,35]. As shown in Fig.…”

“…With excitation at k ex > 300 nm, both 1 and 2 emit brightly yellow to orange Table 3 UV-Vis absorption data of 1-8. state, mixed probably with some character from p(C"Cbpy/ C"CbpyC"C) ? p * (Bu t 3 tpy) 3 [LLCT] transition [19,20,24,25,34,35]. The emission of 2 occurs at a lower energy compared with that of 1 in both solid state (Fig.…”

“…By judicious modification of substituents in the terpyridyl and/or alkynyl ligands, the light emitting colors are changeable [17][18][19][20][21][22][23]. The intense light absorption character in UV-Vis region makes them act as excellent light-harvesting antennae to photosensitize d-block metal emitting or lanthanide luminescence [16,[24][25][26]. Particularly, as a consequence of Pt ?…”