Abstract
Molecular-level chromophore-quencher assemblies have been prepared in precast chlorosulfonated polystyrene ([-CH2CH(p-C6H4SO2Cl)]x-; PS-SO2Cl) films by (1) exposing the intact film to solutions containing the chromophore [(bpy)2Ru(5-NH2Phen)][PF6]2 (bpy is 2,2′-bipyridine; 5-NH2phen is 5-amino-1,10-phenanthroline) which becomes chemically bound through sulfonamide bond formation, (2) partially hydrolyzing a portion of the remaining -SO2Cl sites to -SO3- sites and exposing the resulting films to acetonitrile solutions containing the electron-transfer quencher paraquat (PQ2+) and the reductive scavenger triethanolamine (N(C2H4OH)3). The photophysical properties of the chromophore-based metal-to-ligand charge-transfer excited state have been investigated by lifetime and visible absorption and emission spectra. Although similar to related monomers, excited-state decay in the films is nonexponential. The dynamics of excited-state quenching by PQ2+ following pulsed laser excitation show that the chromophore occupies three different chemical sites within the films. At one site, which accounts for ∼50% of the emitted light and appears to be located near ion channels created by hydrolysis, quenching is rapid, KSV ∼ 6.8 × 104 M-1. A second site exists that undergoes relatively slow quenching, KSV ∼ 3 × 103 M-1, and then only with added [NEt4](ClO4). A third site is present that is not quenched.
| Original language | English |
|---|---|
| Pages (from-to) | 294-304 |
| Number of pages | 11 |
| Journal | Journal of Physical Chemistry |
| Volume | 93 |
| Issue number | 1 |
| Publication status | Published - 1989 |
Fingerprint
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
Photoeffects in thin-film molecular-level chromophore-quencher assemblies. 1. Physical characterization. / Surridge, Nigel A.; McClanahan, Stephen F.; Hupp, Joseph T; Danielson, Earl; Gould, Sharon; Meyer, Thomas J.
In: Journal of Physical Chemistry, Vol. 93, No. 1, 1989, p. 294-304.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Photoeffects in thin-film molecular-level chromophore-quencher assemblies. 1. Physical characterization
AU - Surridge, Nigel A.
AU - McClanahan, Stephen F.
AU - Hupp, Joseph T
AU - Danielson, Earl
AU - Gould, Sharon
AU - Meyer, Thomas J.
PY - 1989
Y1 - 1989
N2 - Molecular-level chromophore-quencher assemblies have been prepared in precast chlorosulfonated polystyrene ([-CH2CH(p-C6H4SO2Cl)]x-; PS-SO2Cl) films by (1) exposing the intact film to solutions containing the chromophore [(bpy)2Ru(5-NH2Phen)][PF6]2 (bpy is 2,2′-bipyridine; 5-NH2phen is 5-amino-1,10-phenanthroline) which becomes chemically bound through sulfonamide bond formation, (2) partially hydrolyzing a portion of the remaining -SO2Cl sites to -SO3- sites and exposing the resulting films to acetonitrile solutions containing the electron-transfer quencher paraquat (PQ2+) and the reductive scavenger triethanolamine (N(C2H4OH)3). The photophysical properties of the chromophore-based metal-to-ligand charge-transfer excited state have been investigated by lifetime and visible absorption and emission spectra. Although similar to related monomers, excited-state decay in the films is nonexponential. The dynamics of excited-state quenching by PQ2+ following pulsed laser excitation show that the chromophore occupies three different chemical sites within the films. At one site, which accounts for ∼50% of the emitted light and appears to be located near ion channels created by hydrolysis, quenching is rapid, KSV ∼ 6.8 × 104 M-1. A second site exists that undergoes relatively slow quenching, KSV ∼ 3 × 103 M-1, and then only with added [NEt4](ClO4). A third site is present that is not quenched.
AB - Molecular-level chromophore-quencher assemblies have been prepared in precast chlorosulfonated polystyrene ([-CH2CH(p-C6H4SO2Cl)]x-; PS-SO2Cl) films by (1) exposing the intact film to solutions containing the chromophore [(bpy)2Ru(5-NH2Phen)][PF6]2 (bpy is 2,2′-bipyridine; 5-NH2phen is 5-amino-1,10-phenanthroline) which becomes chemically bound through sulfonamide bond formation, (2) partially hydrolyzing a portion of the remaining -SO2Cl sites to -SO3- sites and exposing the resulting films to acetonitrile solutions containing the electron-transfer quencher paraquat (PQ2+) and the reductive scavenger triethanolamine (N(C2H4OH)3). The photophysical properties of the chromophore-based metal-to-ligand charge-transfer excited state have been investigated by lifetime and visible absorption and emission spectra. Although similar to related monomers, excited-state decay in the films is nonexponential. The dynamics of excited-state quenching by PQ2+ following pulsed laser excitation show that the chromophore occupies three different chemical sites within the films. At one site, which accounts for ∼50% of the emitted light and appears to be located near ion channels created by hydrolysis, quenching is rapid, KSV ∼ 6.8 × 104 M-1. A second site exists that undergoes relatively slow quenching, KSV ∼ 3 × 103 M-1, and then only with added [NEt4](ClO4). A third site is present that is not quenched.
UR - http://www.scopus.com/inward/record.url?scp=0000816222&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0000816222&partnerID=8YFLogxK
M3 - Article
VL - 93
SP - 294
EP - 304
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 1
ER -