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

ABSTRACT: 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 CHCl₃ 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.

SUBMITTER: Breza M 

PROVIDER: S-EPMC10974634 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature