Diimines photooxidation

Turro C, Hall DB, Chen W, Zuilhof H, Barton JK, Turro NJ. Solution photoreactivity of phenanthrenequinone diimine complexes of rhodium and correlations with DNA photocleavage and photooxidation. / Phys Chem A 1998 102 5708-15. 

The long lifetimes of CT excited states of the Pt(diimine)(dithiolate) complexes allow for bimolecular photochemistry, often involving oxidation of the complex. The earliest report of photoreactivity of these complexes dealt with the photooxidation of Pt(bpy)(tdt) (20) following excitation at 577 nm in chloroform (118). The reaction proceeds with a quantum yield of < ) = 0.03 and was attributed to ET to the halocarbon solvent (Eq. 8) similar to the CTTS photooxidation chemistry of the platinum bis(dithiolate) dianions described above. 

In view of the strong photooxidizing properties of [Re(CO)3(phen)(im)] +, azurin from Pseudomonas aeruginosa has been modified with a rhenium diimine unit via a histidine residue to give... 

The photooxidations of (dbbpy)Pt(edt) and (dbbpy)Pt(dpdt) were studied by Schanze and co-workers [91]. These (diimine)Pt(dithiolate) conq>lexes are room temperature emitters with a LLCT assigned excited state (see Section V and Table lb). (dbbpy)Pt(edt) is photooxidized upon irradiation in aerated solution to the corresponding sulfinate, disulfinate, and bis(sulfenate) conqrlexes (Scheme S). In contrast, (dbbpy)Pt(dpdt) is photooxidized upon irradiation in aerated solution to generate the 1,2-enedithiolate complex (dbbpy)Pt(S2C2l%2) (Scheme S). 

---