Structures and photochemistry of inclusion compounds of 9,10-dihydro-9,10-ethenoanthracene-11,12-bis(diphenylphosphine oxide)

Inclusion complexes of 9,10-dihydro-9,10-ethenoanthracene-11,12-bis(diphenylphosphine oxide) (1) as host are synthesized using a variety of guest solvent molecules and the photochemistry of the host molecule is studied in solution and in the crystalline complexes. The crystal structures of four complexes are determined and correlated with their photochemical reactivity. In each case only one dibenzosemibullvalene photoproduct is obtained in the photolysis. Since three of the complexes studied crystallize in the chiral space group P2(1)2(1)2(1), irradiation of single crystals produces a chiral photoproduct in >90% enantiomeric excess. Determination of the absolute configurations of reactants and products allows elucidation of the key structural features that control the enantiospecific solid-state photorearrangements.