Photochemistry and photophysical properties of novel, unsymmetrically substituted metallophthalocyanines.

A series of novel, unsymmetrically substituted metallo-phthalocyanines was synthesized, along with their symmetrically substituted analogs, and the effects of structure and metal substitution on their photophysical and photoredox properties were investigated. The macrocycles were synthesized using a mixed-condensation method followed by chromatographic separation of the resulting soluble products. They possess a catechol "active site" and three tert-butyl groups for enhanced solubility. The ground- and excited-state photophysical properties of the free-base, Zn(II) and Pd(II) macrocycles were measured and compared with their symmetrically substituted (tetra[tert-butyl]) analogs. The efficiency with which these macrocycles sensitize the formation of singlet oxygen was determined and discussed in the context of the excited-state photophysical properties. Several examples of photoinduced electron transfer reactions with one- and two-electron acceptors are demonstrated and discussed. These soluble molecules can be tuned to optimize their photochemical and redox properties by varying the central metal, axial ligands and other substituents, thereby providing a series of molecules for the investigation of photodynamic therapy and photoinduced electron transfer mechanisms.