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]n (n = 0, 1)

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Keith Man-Chung Wong
  • Sally Chan-Fung Lam
  • Nianyong Zhu
  • Vivian Wing-Wah Yam
  • Séverine Roué
  • Claude Lapinte
  • Sofiane Fathallah
  • Karine Costuas
  • Samia Kahlal
  • Jean-François Halet

Detail(s)

Original languageEnglish
Pages (from-to)7086-7097
Journal / PublicationInorganic Chemistry
Volume42
Issue number22
Publication statusPublished - 3 Nov 2003
Externally publishedYes

Abstract

A novel heterobimetallic alkynyl-bridged complex, [Re(bpy)(CO) 3(C≡C-C6H4-C≡C)Fe(C 5Me5)(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-C6H 4-(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-C 6H4-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-C 6H4-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.

Citation Format(s)

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]n (n = 0, 1). / Wong, Keith Man-Chung; Lam, Sally Chan-Fung; Ko, Chi-Chiu; Zhu, Nianyong; Yam, Vivian Wing-Wah; Roué, Séverine; Lapinte, Claude; Fathallah, Sofiane; Costuas, Karine; Kahlal, Samia; Halet, Jean-François.

In: Inorganic Chemistry, Vol. 42, No. 22, 03.11.2003, p. 7086-7097.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review