A greener route to blue: solid-state synthesis of phthalocyanines Daniel Langerreiter, Mauri Kostiainen,Sandra Kaabe and, Eduardo Anaya Plaza Department of Bioproducts and Biosystems Aalto University, Finland Sustainability and environmentally friendly alternatives of producing and synthesizing chemicals are gaining more importance and are heavily investigated, aligned with the UN sustainable development goals #6 and #12 – clean water and sanitation, and responsible consumption and production, respectively. A greener route to achieve these goals relies on solid-state reactions, where solvents are drastically reduced. [1] Especially mechanochemistry [2,3] has gained importance, not just in organic synthesis but also in polymer science or material chemistry. [4–6] One field which might benefit from a greener synthesis pathway is the synthesis of organic dyes, where water- miscible, high-boiling point solvents are still widely used. Mechanochemical and solid-state synthesis of dyes provide an opportunity for avoiding the use of a large amount of solvent, which could be a threat to water quality and the environment, while bringing economic benefits to industry. Within the organic dyes, phthalocyanines (Pcs) are one of the most famous onea [7] , with a broad applicability in optoelectronics, catalysis, sensing and nanomedicine. [8,9] At the current state, 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 synthesis of phthalocyanines, in which we reduce up to 100- fold the amount of the solvent. Through systematic screening of various reaction parameters, carried out by ball- milling and aging, we show the influence the different variables like temperature, presence of a template, and the amount and role of DMAE in the conversion of t Bu phthalonitrile to tetra- t Bu phthalocyanine. References 1. K. Tanaka, F. Toda, Chem. Rev. 2000 , 100 , 1025–1074. 2. V. Štrukil, M. D. Igrc, L. Fábián, M. Eckert-Maksić, S. L. Childs, D. G. Reid, M. J. Duer, I. Halasz, C. Mottillo, T. Friščić, Green Chem. 2012 , 14 , 2462. 3. S. L. James, C. J. Adams, C. Bolm, D. Braga, P. Collier, T. Friščić, F. Grepioni, K. D. M. Harris, G. Hyett, W. Jones, A. Krebs, J. Mack, L. Maini, A. G. Orpen, I. P. Parkin, W. C. Shearouse, J. W. Steed, D. C. Waddell, Chem. Soc. Rev. 2012 , 41 , 413–447. 4. S. Tanaka, in Met. Fram. Biomed. Appl. , Elsevier, 2020 , pp. 197–222. 5. A. Krusenbaum, S. Grätz, G. T. Tigineh, L. Borchardt, J. G. Kim, Chem. Soc. Rev. 2022 , 51 , 2873–2905. 6. X. Li, M. Baldini, T. Wang, B. Chen, E. Xu, B. Vermilyea, V. H. Crespi, R. Hoffmann, J. J. Molaison, C. A. Tulk, M. Guthrie, S. Sinogeikin, J. V. Badding, J. Am. Chem. Soc. 2017 , 139 , 16343–16349. 7. M. O. Senge, N. N. Sergeeva, K. J. Hale, Chem. Soc. Rev. 2021 , 50 , 4730–4789. 8. M. Urbani, G. de la Torre, M. K. Nazeeruddin, T. Torres, Chem. Soc. Rev. 2019 , 48 , 2738–2766. 9. M. Wang, K. Torbensen, D. Salvatore, S. Ren, D. Joulié, F. Dumoulin, D. Mendoza, B. Lassalle-Kaiser, U. Işci, C. P. Berlinguette, M. Robert, Nat. Commun. 2019 , 10 , 3602.
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