Photolysis of (Halomethyl)naphthalenes: An Investigation of the Heterolysis and Homolysis of Carbon-Halogen Bonds in (Arylmethyl)halides

The photolysis of (halomethyl)naphthalenes in methanol and cyclohexane was examined by means of product and quantum yield studies, sensitization and quenching experiments, and the technique of transient absorption spectroscopy. Evidence is presented for three modes of heterolytic bond cleavage. The first originates from an excited singlet state, and may be direct or may involve an exciplex formed during sensitization. The second mode is through an exciplex of the (halomethyl)naphthalene and a triplet sensitizer. The third mode appears to be important only for (iodomethyl)naphthalene (19I) and involves formation of a complex between ground state 19I and atomic iodine which gives solvolysis product and diiodide radical ion on reaction with methanol. The triplet (halomethyl)naphthalenes are found to be unreactive. Carbon-halogen bond homolysis occurs apparently both from the direct photolysis and from sensitization via exciplex formation.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Slocum, Gregory Howard

• Chemistry, Organic

Identifier

(UMI)AAI8409835

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70239