title: Anomalous reactivity of radical cations produced by photosensitized oxidation of 4-methoxybenzyl alcohol derivatives: role of the sensitizer.
abstract: Steady-state and nanosecond laser flash photolysis measurements of 4-methoxybenzyl alcohol (1a), 4-methoxy-alpha-methylbenzyl alcohol (1b), 4,4'-dimethoxydiphenylmethanol (1c) and 4-methoxy-alpha,alpha'-dimethylbenzyl alcohol (1d) were carried out in air-equilibrated CH(2)Cl(2) and CH(3)CN solutions, in the presence of 9,10-dicyanoanthracene (DCA) and N-methylquinolinium tetrafluoroborate (NMQ(+)BF(4)(-)) as sensitizers. In particular, steady-state irradiation with DCA produced carbonyl compounds and, with NMQ(+)BF(4)(-), carbonyl compounds, ethers (substrates 1a-c ) and styrene (substrate 1d ) while time-resolved investigations gave evidence of charged species produced upon irradiation. The effect of solvent polarity on the reactivity was investigated; in the case of DCA, the reactivity increased with the solvent polarity, while the opposite was obtained when NMQ(+)BF(4)(-) was used. Quantum mechanical calculations at semiempirical (INDO/1-CI) and DFT (B3LYP/6-311G(d)) levels were used to support transient assignments and to obtain the charge and spin density distributions, respectively. The different photooxidation mechanisms operative with the neutral and charged sensitizer were rationalized in terms of the reactivity of free and complexed radical cations, respectively.
authors: Dipartimento di Chimica and Centro di Eccellenza Materiali Innovativi Nanostrutturati (CEMIN), Università di Perugia, Via Elce di Sotto 8, 06123, Perugia, Italy. dgiacco@unipg.it
authors: Tiziana
authors: T
authors: Del Giacco
authors: Annalisa
authors: A
authors: Faltoni
authors: Fausto
authors: F
authors: Elisei
mesh_terms: D000840:Anisoles / Q000737:chemistry / Q000528:radiation effects*; D000873:Anthracenes / Q000737:chemistry* / Q000528:radiation effects; D002412:Cations / Q000737:chemistry; D005453:Fluorescence; D005609:Free Radicals / Q000737:chemistry / Q000528:radiation effects; D007834:Lasers; D008956:Models, Chemical; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry* / Q000528:radiation effects; D010084:Oxidation-Reduction; D010777:Photochemistry; D010782:Photolysis; D011789:Quantum Theory; D011806:Quinolinium Compounds / Q000737:chemistry* / Q000528:radiation effects; D012680:Sensitivity and Specificity; D012997:Solvents / Q000737:chemistry / Q000528:radiation effects
chemical_list: C521244:9,10-dicyanoanthracene; D000840:Anisoles; D000873:Anthracenes; D002412:Cations; D005609:Free Radicals; D009570:Nitriles; D011806:Quinolinium Compounds; D012997:Solvents; C026557:1-methylquinolinium; C066943:anisyl alcohol