Photochemical energy storage (photosensitized isomerization of norbornadiene to quadricyclane by copper (I) complexes). Doctoral thesis

Technical Report · Sat Jan 01 04:00:00 EST 1983

OSTI ID:5354870

Fife, D J

This research has focused on the sensitized photoisomerization step of a solar energy storage system based on the interconversion of norbornadiene (NBD) and quadricyclane (Q). Sensitizers studied in the photoisomerization were arylphosphine complexes of copper(I) halides (Ph/sub 3/numbernumbernumberP)/sub 3/CuX, (MePh/sub 2/P)/sub 3/CuX, (DIPHOS)CuC/sub 1/; X = C1, Br, I and DIPHOS = Ph/sub 2/P(CH/sub 2/)/sub 2/PPh/sub 2/). The lowest electronic excited state of the complexes can be an effective triplet energy sensitizer as evidenced by a maximum quantum yield of 1.0 with (MePh/sub 3/''P)/sub 3/CuX. The sensitization mechanism of the L3CuX complexes is proposed as a bimolecular energy transfer process in which energy transfer takes place through the metal centered orbitals. The efficiency of the (MePh/sub 2/P)/sub 3/CuX sensitizers is unprecedented by other reported inorganic or organic sensitizers; however, ligand dissociation of the complexes in dilute solutions detracts from their otherwise attractive features. The free ligands undergo rapid photodecomposition and are extremely poor sensitizers of the NBD/Q system.

• Research Organization: Air Force Inst. of Tech., Wright-Patterson AFB, OH (USA)
• OSTI ID: 5354870
• Report Number(s): AD-A-135363/0
• Country of Publication: United States
• Language: English

Related Subjects

14 SOLAR ENERGY
140505* -- Solar Energy Conversion-- Photochemical
Photobiological
& Thermochemical Conversion-- (1980-)
ABSORPTION
ARYL RADICALS
CHEMICAL REACTIONS
CONVERSION
COPPER COMPOUNDS
DIENES
ENERGY CONVERSION
ENERGY STORAGE
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXCITATION
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
ISOMERIZATION
LIGANDS
MOLECULES
ORGANIC COMPOUNDS
PHOTOCHEMICAL ENERGY STORAGE
PHOTOCHEMICAL REACTIONS
PHOTOSENSITIVITY
POLYENES
RADICALS
SENSITIVITY
STORAGE
TRANSITION ELEMENT COMPOUNDS