A Greener Route to Blue: Solid-State Synthesis of Phthalocyanines

Abstract

Phthalocyanines are important organic dyes with a broad applicability in optoelectronics, catalysis, sensing and nanomedicine. Currently, phthalocyanines are synthetized in high boiling organic solvents, like dimethylaminoethanol (DMAE), which is a flammable, corrosive, and bioactive substance, miscible with water and harmful to the environment. Here we show a new solid-state approach for the high-yielding synthesis of phthalocyanines, which reduces up to 100-fold the amount of DMAE. Through systematic screening of solid-state reaction parameters, carried out by ball-milling and aging, we reveal the influence of key variables—temperature, presence of a template, and the amount and role of DMAE in the conversion of tBu phthalonitrile to tetra-tBu phthalocyanine. These results set the foundations to synthesize these high-performance dyes through a greener approach, opening the field of solid-state synthesis to a wider family of phthalocyanines.