DFT Studies of Dimethylaminophenyl-Substituted Phthalocyanine and Its Silver Complexes.

The dimethylaminophenyl-substituted silver phthalocyanine [dmaphPcAg] can be used as a UV-vis photoinitiator for in situ preparation of a silver/polymer nanocomposite. To verify early steps of the supposed mechanism of radical polymerization, we performed quantum chemical calculations of m [dmaphPcAg] q complexes with charges q = +1 to -2 in the two lowest spin states m, of a free ligand and its dehydrogenated/deprotonated products m [dmaphPcH n ] q , n = 2 to 0, q = 0, -1 or -2, in the lowest spin states m. The calculated electronic structures and electron transitions of all the optimized structures in CHCl 3 solutions are compared with experimental EPR and UV-vis spectra, respectively. The unstable 3 [dmaphPcAg] + species deduced only from previous EPR spin trap experiments was identified. In addition to 2 [dmaphPcAg] 0 , our results suggest the coexistence of both reaction intermediates 1 [dmaphPcAg] - and 3 [dmaphPcAg] - in reaction solutions. Silver nanoparticle formation is a weak point of the supposed reaction mechanism from the energetic, stereochemistry, and electronic structure points of view.