Radiation chemical and photophysical properties of C-60(C4H8SO3Na)(n) in aqueous solution: A laser flash photolysis and pulse radiolysis study

Citation
H. Mohan et al., Radiation chemical and photophysical properties of C-60(C4H8SO3Na)(n) in aqueous solution: A laser flash photolysis and pulse radiolysis study, FUL SCI TEC, 9(1), 2001, pp. 37-53
Citations number
47
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
FULLERENE SCIENCE AND TECHNOLOGY
ISSN journal
1064122X → ACNP
Volume
9
Issue
1
Year of publication
2001
Pages
37 - 53
Database
ISI
SICI code
1064-122X(2001)9:1<37:RCAPPO>2.0.ZU;2-Z
Abstract
Optical absorption studies on aqueous solutions of C-60(C4H8SO3Na)(n) (n = 4-6) revealed deviation from the Beer-Lambert law in the 250-350 nm region, which is assigned to the formation of solute aggregates at concentrations higher than 1 x 10(-3) mol dm(-3). Dynamic light scattering experiments sho wed aggregates with an average size of similar to 100 nm. The solute has a broad weak fluorescence emission (phi (f) = 1.8 x 10(-3)) in the 450-650 nm region, which remained independent of solute concentration. The broad tran sient absorption band in the 450-900 nm region (epsilon (660) = 2170 dm(3) mol(-1) cm(-1)), which formed immediately on laser flash photolysis (lambda (ex) = 355 nm, 35 ps), is assigned to singlet-singlet transition. It decay s to a tripler excited state whose absorption is observed to depend strongl y on salute concentration. In dilute solutions, an absorption band with lam bda (max) = 590 nm is seen, and at high solute concentration a broad absorp tion in the 500-900 nm region is observed. The e(aq)(-) reacts with the sol ute with a bimolecular rate constant of 1.7 x 10(8) dm(3) mol(-1) s(-1) and forms weak broad absorption bands at 440, 540, 670, 870, 940, and 1020 nm. Isopropanol radicals also react with the solute with a bimolecular rate co nstant of 2.3 x 10(8) dm(3) mol(-1) s(-1) with the formation of a transient optical absorption spectrum similar to that observed on reaction with e(aq )(-) and assigned to a solute radical anion. Thr H-. and (OH)-O-. radicals react with bimolecular rate constants of 3.2 x 10(9) and 4.4 x 109 dm(3) mo l(-1) s(-1), respectively, and form transient absorption bands at 440, 510, and 660 nm. Based on electron transfer studies with suitable electron dono r/acceptor substrates, the ranges of the reduction and oxidation potentials of the solute an estimated.