Influence of a gold(I)-acetylide subunit on the photophysics of Re(phen)(CO) 3Cl

Irina E. Pomestchenko, Dmitry Polyansky, Felix N. Castellano

Research output: Contribution to journalArticle

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Abstract

The synthesis and photophysical properties of two new Re(l) complexes are reported: fac-Re(phenC≡CH)(CO) 3Cl (where phenC≡CH is 5-ethynyl-1,10-phenanthroline) and its Au(l)-acetylide analogue (fac-Re(phenC≡CAuPPh 3)(CO) 3-Cl). Also reported are the photophysical measurements obtained for the benchmark fac-Re(phen)(CO) 3Cl chromophore, as well as the phenC≡CAuPPh 3 and phenC≡CH ligands. The unstable nature of the precursor gold-containing ligand illustrates the advantage of using the "chemistry on the complex" approach, which facilitated preparation of the Re-Au binuclear complex. Where possible, all compounds were studied by static and transient absorption (TA), as well as steady-state and time-resolved photoluminescence (TRPL), at room temperature (RT) and 77 K, as well as nanosecond time-resolved infrared (TRIR) spectroscopy. The spectroscopic information provided by these techniques enabled a thorough evaluation of excited-state decay in most cases. In fac-Re(phenC≡CH)-(CO) 3Cl, the RT excited-state decay is most consistent with a metal-to-ligand charge transfer (MLCT) assignment, whereas at 77 K, the lowest excited state is dominated by the triplet intraligand ( 3IL) state, localized within the diimine ligand. The lowest excited state in fac-Re(phenC≡CAuPPh 3)(CO) 3Cl seems to result from an admixture of Re-based MLCT and 3IL states resident on the phenC≡CAuPPh 3 moiety. TA and TRIR methods indicate that these excited states are thermally equilibrated at room temperature. At 77 K, the MLCT energy of fac-Re(phen-C≡CAuPPh 3)(CO) 3Cl is increased as a result of the glassy medium and the resulting excited state can be considered to be ligand-localized.

Original languageEnglish
Pages (from-to)3412-3421
Number of pages10
JournalInorganic Chemistry
Volume44
Issue number10
DOIs
Publication statusPublished - May 16 2005

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Carbon Monoxide
Gold
Excited states
gold
Ligands
ligands
excitation
Charge transfer
Metals
charge transfer
room temperature
metals
decay
Chromophores
admixtures
Temperature
chromophores
Infrared spectroscopy
Photoluminescence
infrared spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Influence of a gold(I)-acetylide subunit on the photophysics of Re(phen)(CO) 3Cl. / Pomestchenko, Irina E.; Polyansky, Dmitry; Castellano, Felix N.

In: Inorganic Chemistry, Vol. 44, No. 10, 16.05.2005, p. 3412-3421.

Research output: Contribution to journalArticle

Pomestchenko, Irina E. ; Polyansky, Dmitry ; Castellano, Felix N. / Influence of a gold(I)-acetylide subunit on the photophysics of Re(phen)(CO) 3Cl. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 10. pp. 3412-3421.
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