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 language | English |
|---|---|
| Pages (from-to) | 3412-3421 |
| Number of pages | 10 |
| Journal | Inorganic Chemistry |
| Volume | 44 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - May 16 2005 |
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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 journal › Article
}
TY - JOUR
T1 - Influence of a gold(I)-acetylide subunit on the photophysics of Re(phen)(CO) 3Cl
AU - Pomestchenko, Irina E.
AU - Polyansky, Dmitry
AU - Castellano, Felix N.
PY - 2005/5/16
Y1 - 2005/5/16
N2 - 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.
AB - 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.
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U2 - 10.1021/ic048376r
DO - 10.1021/ic048376r
M3 - Article
VL - 44
SP - 3412
EP - 3421
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 10
ER -