2 + 2 MAKES A POLYMER: CATALYSED HETEROATOMIC DIELS-ALDER REACTIONS TO MAKE NEW POLY(FULLERENE)S

Vitor Fernandes Moreno; Maria Eduarda Rocha Santos Medina; Roger Clive Hiorns; Luiz Carlos da Silva Filho

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Trabalho

Título do Trabalho

2 + 2 MAKES A POLYMER: CATALYSED HETEROATOMIC DIELS-ALDER REACTIONS TO MAKE NEW POLY(FULLERENE)S

Autores

Vitor Fernandes Moreno
Maria Eduarda Rocha Santos Medina
Roger Clive Hiorns
Luiz Carlos da Silva Filho

Modalidade

Pôster - resumo

Área temática

Dispositivos optoeletrônicos

Data de Publicação

27/05/2026

País da Publicação

Brasil

Idioma da Publicação

pt-BR

Página do Trabalho

https://www.even3.com.br/anais/workshop-do-ineo-2026/1459624-2--2-makes-a-polymer--catalysed-heteroatomic-diels-alder-reactions-to-make-new-poly(fullerene)s

ISBN

978-65-272-2467-9

Palavras-Chave

Quinoline derivatives, Diels-Alder reaction, polyfullerenes, OPV, PCBM

Resumo

Over the past few years, fullerenes and their derivatives have constituted a pivotal class of materials for the development of organic photovoltaic devices (OPVs), owing to their remarkable versatility, particularly in the design of advanced compounds that exploit their high electron affinity and superior electron-accepting capability [1-3]. The practical application of pristine C60 is frequently limited by its low solubility in common organic solvents, as well as its pronounced tendency toward aggregation and crystallization [4]. These factors significantly deteriorate the morphology of the active layer and progressively impair device performance. In this context, numerous synthetic strategies have been developed to promote the chemical functionalization and reactivity of this carbon allotrope. Main-chain poly(fullerene)s (PFs) have emerged as a strategic alternative, integrating the outstanding electronic properties of fullerenes with the processability and film-forming characteristics of polymeric systems, thereby mitigating undesirable phase segregation. The most widely employed synthetic approaches for these materials typically rely on radical-based methodologies, such as atom transfer radical addition polymerization (ATRP), as well as cycloaddition reactions including Diels–Alder and Prato chemistry [5-7]. In this work, an innovative synthetic route was proposed for the preparation of versatile poly(fullerene)s via the reaction of newly designed quinoline derivatives with C60 and PCBM. The selection of quinoline units as comonomers is grounded in their donor–p–acceptor (D–p–A) architecture, which is well recognized for promoting enhanced thermal stability and efficient p-conjugation. The polymerization reaction was catalyzed by dichloro[1,3-bis(diphenylphosphino)propane]nickel(II) ([Ni(dppp)Cl2]). The most notable feature of this synthetic methodology is its mechanistic pathway, proceeding through a [2+2] cycloaddition—an unprecedented route in the literature for the formation of fullerene-based polymers—thus distinguishing it from conventional strategies such as ATRAP or Diels–Alder reactions. Structural characterization of the resulting copolymers was successfully performed using one- and two-dimensional Nuclear Magnetic Resonance (¹H and ¹³C NMR, including 2D experiments), together with Gel Permeation Chromatography (GPC), which confirmed polymer chain growth and effective incorporation of the designed functional groups. Additionally, optoelectronic properties were investigated by cyclic voltammetry. The electrochemical data revealed a significant enhancement in the redox response of quinoline-containing systems compared to non-functionalized analogues, corroborating the beneficial impact of the D–p–A molecular architecture on electronic modulation. Accordingly, this study establishes not only an efficient and original protocol for the synthesis of poly(fullerene)s but also provides a promising framework for the incorporation of other conjugated molecules via catalytic coupling strategies, targeting next-generation high-performance organic electronic devices. References 1- Li, G.; Zhu, R.; Yang, Y. Polymer solar cells. Nat. Photonics 2012, 6, 153–161. 2 - Hovel, H. J. (1975). Solar cells. NASA STI/Recon Technical Report A, 76, 20650. 3 - Grätzel, M. (2009). Recent advances in sensitized mesoscopic solar cells. Accounts of chemical research, 42(11), 1788-1798. 4 - He, Y.; Li, Y. Fullerene derivative acceptors for high performance polymer solar cells. Phys. Chem. Chem. Phys. 2011, 13, 1970–1983. 5 -Hirsch, A. Functionalization of Single-Walled Carbon Nanotubes and Fullerenes. Angew. Chem. Int. Ed. 2002, 41, 1853–1859. 6 - Santos Silva, H., et. al. (2017). Oligo-and poly (fullerene) s for photovoltaic applications: Modeled electronic behaviors and synthesis. Journal of Polymer Science Part A: Polymer Chemistry, 55(8), 1345-1355. 7- Batagianni, E., et. al. (2025). Radical and environmentally friendly route to poly(fullerene)s incorporating C60, C70, and PCBM. Macromolecules, 58(3), 1686–1704. https://doi.org/10.1021/acs.macromol.4c02154. Acknowledgments The authors would like to thank Instituto Nacional de eletrônica Orgãnica (INEO), Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) [Grant numbers 2025/27044-5, 2024/14443-6 and 2024/02935-1], and Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) [Grant numbers, 303750/2024-3, 408449/2024-1].

Título do Evento: Workshop do INEO 2026
Cidade do Evento: Nazaré Paulista
Título dos Anais do Evento: Anais do Workshop do INEO 2026
Nome da Editora: Even3
Meio de Divulgação: Meio Digital

Como citar

MORENO, Vitor Fernandes et al.. 2 + 2 MAKES A POLYMER: CATALYSED HETEROATOMIC DIELS-ALDER REACTIONS TO MAKE NEW POLY(FULLERENE)S.. In: Anais do Workshop do INEO 2026. Anais...Nazaré Paulista(SP) Hotel Estância Atibainha, 2026. Disponível em: https//www.even3.com.br/anais/workshop-do-ineo-2026/1459624-2--2-MAKES-A-POLYMER--CATALYSED-HETEROATOMIC-DIELS-ALDER-REACTIONS-TO-MAKE-NEW-POLY(FULLERENE)S. Acesso em: 10/08/2026