Laser flash photolysis studies on hydrogen atom abstraction from phenol by triplet naphthoquinones in acetonitrile

Abstract

By means of ns laser flash photolysis, the absorption spectra and molar absorption coefficients (Iµ) of the 1,4-naphthosemiquinone radical (NQH˙) and 2,3-dimethyl-1,4-naphthosemiquinone radical (DMNQH˙) have been determined to be 8200 dm3 mol–1 cm–1 at 365 nm and 7100 dm3 mol–1 cm–1 at 368 nm in acetonitrile (MeCN) and MeCN–H2O (4 : 1 v/v) at 295 K. On the basis of the determined absorption spectra and Iµ values, hydrogen atom abstraction (HA) by triplet 1,4-naphthoquinone (NQ) and 2,3-dimethyl-1,4-naphthoquinone (DMNQ) from phenol (PhOH) in MeCN was studied by laser photolysis techniques. It was found that HA by triplet NQ and DMNQ (3NQ* and 3DMNQ*) from PhOH occurred in a collision process with quenching rate constants, kq= 8.6 × 109 and 5.5 × 108 dm3 mol–1 s–1, respectively. On the basis of the obtained values of kq and quantum yields (ΦHA), the efficiencies (ψHA) for HA by both 3NQ* and 3DMNQ* from PhOH were obtained to be unity. The rate constants (kHA) for HA of 3NQ* and 3DMNA* were determined to be 8.6 × 109 and 5.5 × 108 dm3 mol–1 s–1, respectively. The difference in kHA may be derived from (1) the steric hindrance by the methyl groups of DMNQ and (2) the degree of 3(π,π*) character mixed in with the 3(n,π*) of NA and DMNQ. The triplet–triplet absorption spectra of NQ and DMNQ were identified, and their absolute molar absorption coefficients (IµT–Tλ) were determined to be 8200 dm3 mol–1 cm–1 at 365 nm and 5200 dm3 mol–1 cm–1 at 368 nm, respectively, in MeCN on the basis of the quantum yields of intersystem crossing (Φisc; 0.74 for NQ, 0.98 for DMNQ) evaluated by thermal lensing techniques. The deactivation mechanism of 3NQ* and 3DMNQ* in the absence of PhOH was found to be self-quenching by NQ and DMNQ in MeCN with the rate constants, kSQ= 9.7 × 108 and 1.2 × 108 dm3 mol–1 s–1, respectively.