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

Thesis/Dissertation · Sat Jan 01 04:00:00 EST 1983

OSTI ID:5705076

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/P)/sub 3/CuX, (MePh/sub 2/P)/sub 3/CuX, (DIPHOS)CuCl; X = Cl, 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 2/P)/sub 3/CuX. The sensitization mechanism of the L/sub 3/CuX 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. Photoexcitation of the (NBD) complexes can produce Q but with quantum efficiencies < 1.0. Photophysical properties of the arylphosphines and their copper(I) halide complexes are reported.

• OSTI ID: 5705076
• Country of Publication: United States
• Language: English

Related Subjects

25 ENERGY STORAGE
250800* -- Energy Storage-- Chemical
ALKENES
CHEMICAL REACTIONS
COPPER
CYCLOALKENES
ELEMENTS
ENERGY STORAGE
HYDROCARBONS
ISOMERIZATION
MATERIALS
METALS
NORBORNADIENE
ORGANIC COMPOUNDS
PHOTOCHEMICAL ENERGY STORAGE
PHOTOCHEMICAL REACTIONS
PHOTOSENSITIVITY
QUADRICYCLENE
SENSITIVITY
STORAGE
TRANSITION ELEMENTS