title: Photoinduced omega-bond dissociation of m-halomethylbenzophenones studied by laser photolysis techniques and DFT calculations. Substituted position effects.
abstract: Photochemical profiles of omega-cleavage of carbon-X (X = Br and Cl) bonds in m-bromo- and m-chloromethylbenzophenones (m-BMBP and m-CMBP) were investigated by laser photolysis techniques and DFT calculations. m-BMBP and m-CMBP were found to undergo omega-bond cleavage to yield the m-benzoylbenzyl radical (m-BBR) at 295 K, and the quantum yields were determined. No CIDEP signal was detected upon 308 nm laser photolysis of both the compounds. From these observations, it was inferred that the omega-bond of these m-halomethylbenzophenones (m-HMBP) cleaves in the lowest excited singlet state (S(1)(n,pi(*))) upon direct excitation. Upon triplet sensitization of acetone (Ac), the m-BBR formation was observed in transient absorption for an Ac-m-BMBP system, and an efficiency of the C-Br bond cleavage in the lowest triplet state (T(1)(n,pi(*))) of m-BMBP was determined. In contrast, formation of triplet m-CMBP was seen for an Ac-m-CMBP system. Absence of C-Cl bond cleavage in the triplet state of m-CMBP indicated the reactive state of m-CMBP for omega-cleavage is only the S(1)(n,pi(*)) state. Based on the efficiencies and DFT calculations for excited state energies, photoinduced omega-bond dissociation of m- and p-HMBPs was characterized.
authors.affiliation: Department of Chemistry, Gunma University, Kiryu 376-8515, Japan. yamaji@chem-bio.gunma-u.ac.jp
authors.forename: Minoru
authors.initials: M
authors.lastname: Yamaji
authors.forename: Michiyo
authors.initials: M
authors.lastname: Ogasawara
authors.forename: Kazuhiro
authors.initials: K
authors.lastname: Kikuchi
authors.forename: Satoru
authors.initials: S
authors.lastname: Nakajima
authors.forename: Shozo
authors.initials: S
authors.lastname: Tero-Kubota
authors.forename: Bronislaw
authors.initials: B
authors.lastname: Marciniak
authors.forename: Koichi
authors.initials: K
authors.lastname: Nozaki
mesh_terms: D000096:Acetone / Q000737:chemistry; D000465:Algorithms; D001577:Benzophenones / Q000737:chemistry*; D001966:Bromine / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D002713:Chlorine / Q000737:chemistry; D006846:Hydrocarbons, Halogenated / Q000737:chemistry*; D010777:Photochemistry / Q000379:methods*; D010782:Photolysis; D011789:Quantum Theory; D013053:Spectrophotometry; D013696:Temperature
chemical_list: D001577:Benzophenones; D006846:Hydrocarbons, Halogenated; D000096:Acetone; D002713:Chlorine; D002244:Carbon; D001966:Bromine