Photobehavior of copper(I) compounds. 4. Role of the triplet state of (arylphosphine)copper(I) complexes in the photosensitized isomerization dienes

Journal Article · Wed Apr 20 00:00:00 EDT 1988 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00281a002· OSTI ID:5832801

Liaw, B; Orchard, S W; Kutal, C

Photoisomerization of cis- and trans-piperylene can be sensitized with high quantum efficiency by Cu(diphos)BH/sub 4/ (diphos is 1,2-bis(diphenylphosphino)ethane) and Cu(prophos)BH/sub 4/ (prophos is 1,3-bis(diphenylphosphino)propane). Sensitization is accompanied by quenching of the emissive /sup 3/(/sigma/-a/sub /pi//) excited state in each copper(I) complex, and the two processes occur with identical Stern-Volmer kinetics. Measurements of the trans/cis diene ratio at the photostationary state can be used to estimate the triplet-state energy as 60-61 kcal for Cu(diphos)BH/sub 4/ and > 61 kcal for Cu(prophos)BH/sub 4/; additional evidence suggests that 66-67 kcal is a reasonable value for the latter complex. Collectively, the results support the assignment of triplet-triplet energy transfer as the primary mechanism for sensitization and quenching in these systems. This mechanism also can accommodate earlier reports that Cu(diphos)BH/sub 4/ and Cu(prophos)BH/sub 4/ sensitize the valence isomerization of norbornadiene to quadricyclene with markedly different quantum efficiencies. 17 refs., 6 figs., 2 tabs.

• Research Organization: Univ. of Georgia, Athens (USA)
• OSTI ID: 5832801
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:8; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
ALKANES
CHEMICAL REACTIONS
CHEMISTRY
COPPER COMPOUNDS
DATA
DIENES
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
ISOMERIZATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PHOTOCHEMISTRY
POLYENES
TRANSITION ELEMENT COMPOUNDS