Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
1299932 | Coordination Chemistry Reviews | 2015 | 12 Pages |
Ru(II) dyads derived from organic units that impart low-lying 3IL excited states combine the most attractive features of organic photosensitizers with those of coordination complexes. The result is a bichromophoric system with excited-state lifetimes that are significantly longer than those associated with traditional 3MLCT states. Incorporation of α-oligothiophenes as the organic chromophore leads to systems that act as dual Type I/II photosensitizers, opening up the possibility of treating hypoxic tumors with photodynamic therapy (PDT) and overcoming problems with in vivo dosimetry. These photosensitizers, particularly those that consist of three thiophene units and higher, are remarkable DNA binders and photocleavers when exposed to light, exhibiting no interference with DNA structural integrity in the absence of a light-trigger. Such light-responsive agents localize in the nuclei of cells without the need for a carrier and produce a potent PDT response with minimal dark toxicity. This phototherapeutic effect translates directly to animals and is superior to the clinical agent Photofrin® in this model. These Ru(II) dyads can be activated with light in the PDT window, despite very low molar extinction coefficients in this region, and this phenomenon can be attributed to the efficiency with which these agents operate. The ability to activate these prodrugs with ultraviolet to near-infrared light marks an unprecedented versatility that can be exploited to match treatment depth to tumor invasion depth without compromising potency, giving rise to photosensitizers for multiwavelength PDT.