Synthesis, characterization and luminescence studies of trinuclear rhenium-cobalt mixed-metal alkynyl complexes containing a tetrahedral CO2C2 cluster unit

The reaction of rhenium(I) diynyl complexes [Re(CO)3(N-N) (C≡C - C≡CH)] [N-N = tBu2bpy (1), bpy (2)] with Co2(CO)8 in THF yielded a new class of luminescent trinuclear rhenium-cobalt mixed-metal alkynyl complexes, [Co2{μ- HC2C≡C[Re(CO)3(N-N)]}(CO)6] [N-N = tBu2bpy (3), bpy (4)]. Their luminescence and electrochemical properties have also been studied. © 2004 Plenum Publishing Corporation.link_to_subscribed_fulltex

Synthesis, electrochemistry and structural characterization of luminescent rhenium(I) monoynyl complexes and their homo- and hetero-metallic binuclear complexes

A series of luminescent rhenium(I) monoynyl complexes, [Re(N-N)(CO)3(C≡C-R)] (N-N = bpy, tBu2bpy; R = C6H5, C6H4-Cl-4, C6H4-OCH3-4, C6H4-C8H17-4, C6H4-C6H5, C8H17, C4H3S, C4H2S-C4H3S, C5H4N), together with their homo- and heterometallic binuclear complexes, {Re(N-N)(CO)3(C≡C-C5H4N)[M]} (N-N = bpy, tBu2bpy; [M] = [Re{(CF3)2-bpy}(CO)3]ClO4, [Re(NO2-phen)(CO)3]ClO4, W(CO)5) have been synthesized and their electrochemical and photoluminescence behaviors determined. The structural characterization and electronic structures of selected complexes have also been studied. The luminescence origin of the rhenium(I) alkynyl complexes has been assigned as derived states of a [dπ(Re) → π*(N-N)] metal-to-ligand charge transfer (MLCT) origin mixed with a [π(C≡CR)→π*(N-N)] ligand-to-ligand charge transfer (LLCT) character. The assignments are further supported by extended Hückel molecular orbital (EHMO) calculations, which show that the LUMO mainly consists of π*(N-N) character while the HOMO is dominated by the antibonding character of the Re-C≡CR moiety resulted from the overlap of the dπ(Re) and π(C≡CR) orbitals. © 2003 Elsevier Science B.V. All rights reserved.link_to_subscribed_fulltex

Luminescent heterometallic branched alkynyl complexes of rhenium(I)-palladium(II): Potential building blocks for heterometallic metallodendrimers

The photophysical and electrochemical behavior of a novel series of luminescent rhenium(I) complexes bearing a trialkynyl ligand, [1,3-(HC≡C)2-5-{(N∧N)(CO)3ReC≡C}C 6H3] (N∧N = tBu2bpy 1, Me 2bpy 2, bpy 3), and their heterometallic branched complexes, [1,3-{Cl(PEt3)2PdC≡C}2-5-{(Nand;N)(CO) 3ReC≡C}C6H3] (N∧N = Me2bpy 4, bpy 5), have been studied; the X-ray crystal structures of 2 and 5 have been determined. Density functional theory calculations have also been carried out in order to probe the bonding in these compounds.link_to_subscribed_fulltex