Radical and Environmentally Friendly Route to Poly(fullerene)s Incorporating C₆₀, C₇₀, and PCBM

Autor(es):Mostrar menos -

Batagianni, Eleftheria ; Doat, Olivier ; Elissalt, Nicolas ; Bouassa, Douvotsu Elisa Moungadji ; Bittencourt, Jessyka Carolina ; Goncalves, Gabriel Cardoso ; Moreno, Vitor Fernandes ; Lima, Joao Victor Morais ; Nogueira, Gabriel Leonardo ; Affonco, Lucas Jorge ; Paulin, Joao Vitor ; Fernandes, Silvia Leticia ; Ferranti, Renato ; Khoukh, Abdel ; da Silva Filho, Luiz Carlos ; Agostini, Deuber Lincon da Silva ; Olivati, Clarissa de Almeida ; Campana, Patricia Targon ; Graeff, Carlos F. O. ; Begue, Didier ; Hiorns, Roger C.

• Tipo de documento: Artigo Científico
• Fonte: MACROMOLECULES; v. 58, n. 3, p. 19-pg., 2025-01-22.

Resumo

For the first time, this article shows how it is possible to make well-soluble poly(fullerene xylene)s using potassium iodide and in low amounts of solvents. This new method makes it possible to use low-cost, environmentally friendly starting materials, nonchlorinated solvents, and main-chain C60, PCBM, and for the first time, C70, polymers. The reaction can even be performed in the presence of water, further increasing its environmental friendliness. Specifically, a dibromomethylated comonomer, such as 2,5-bis(bromomethyl)-1,4-bis(oxidodecyl)benzene, is reacted with potassium iodide, 18-crown-6, and fullerene in refluxing toluene to yield highly modular alternating copolymers. Model reactions show that polymerization works by the transformation of methylene bromides into methylene iodides, which then disintegrate to make methylene radicals that react with the fullerenes. The radical nature of this new iodine-mediated polymerization (IMP) is confirmed by its sensitivity to the radical trap (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO). The comonomers add in pairs to the fullerene to yield linear chains. NMR and UV-visible spectroscopy along with quantum calculations suggest that most bonds to the fullerene are in 1,4-positions on the same hexagonal ring, however, a minority of C60-methylene bonds are situated several bonds apart on the fullerene, suggesting that iodine "walks" across the fullerene surface. This new polymerization of fullerene, without its reliance on copper and chlorinated solvents and ability to work in the presence of water, makes it of wide use for materials for optoelectronics and medicine where even trace impurities can impact heavily on material properties. (AU)

• Processo FAPESP: 20/12356-8 - Otimização da estabilidade de células solares de perovskitas
• Beneficiário: Carlos Frederico de Oliveira Graeff
• Modalidade de apoio: Auxílio à Pesquisa - Temático
• Processo FAPESP: 23/12686-6 - Síntese e caracterização de uma biblioteca de poli(fulereno)s para aplicaçoes fotovoltaicas
• Beneficiário: Carlos Frederico de Oliveira Graeff
• Modalidade de apoio: Auxílio à Pesquisa - Pesquisador Visitante - Internacional
• Processo FAPESP: 13/07296-2 - CDMF - Centro de Desenvolvimento de Materiais Funcionais
• Beneficiário: Elson Longo da Silva
• Modalidade de apoio: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs
• Processo FAPESP: 21/03379-7 - Aplicação de Novos Materiais como Eletrodo em Supercapacitores Flexíveis
• Beneficiário: João Victor Morais Lima
• Modalidade de apoio: Bolsas no Brasil - Doutorado