Photophysics of Cage/Guest Assemblies: Photoinduced Electron Transfer between a Coordination Cage Containing Osmium(II) Luminophores, and Electron-Deficient Bound Guests in the Central Cavity.

A heterometallic octanuclear coordination cage [OsZn(L)]X (denoted Os•Zn; X = perchlorate or chloride) has been prepared (L is a bis-bidentate bridging ligand containing two pyrazolyl-pyridine chelating units separated by a 1,5-naphthalenediyl spacer group). The {Os(NN)} units located at four of the eight vertices of the cube have a long-lived, phosphorescent MLCT excited state which is a stronger electron donor than [Ru(bipy)]. The chloride form of Os•Zn is water-soluble and binds in its central cavity the hydrophobic electron-accepting organic guests 1,2,4,5-tetracyanobenzene, 1,4-naphthoquinone and 1-nitronaphthalene, with binding constants in the range 10-10 M, resulting in quenching of the phosphorescence arising from the Os(II) units. A crystal structure of an isostructural Co cage containing one molecule of 1,2,4,5-tetracyanobenzene as a guest inside the cavity has been determined. Ultrafast transient absorption measurements show formation of a charge-separated Os(III)/guest state arising from cage-to-guest photoinduced electron transfer; this state is formed within 13-21 ps, and decays on a time scale of ca. 200 ps. In the presence of a competing guest with a large binding constant (cycloundecanone) which displaces each electron-accepting quencher from the cage cavity, the charge-separated state is no longer observed. Further, a combination of mononuclear {Os(NN)} model complexes with the same electron-accepting species showed no evidence for formation of charge-separated Os(III)/guest states. These two control experiments indicate that the {Os(NN)} chromophores need to be assembled into the cage structure to bind the electron-accepting guests, and for PET to occur. These results help to pave the way for use of photoactive coordination cages as hosts for photoredox catalysis reactions on bound guests.