Engineering photocatalytic porous organic materials for directing redox versus energy transfer processes

Two organic materials containing phenanthroline and triazine fragments, but connected in different ways, are presented. The imine-based material Phen–Tz–covalent organic framework (COF) preferentially shows photocatalytic activity through an energy transfer pathway as observed for olefin photoisomer...

ver descrição completa

Detalhes bibliográficos
Autores: López Magano, Alberto, Solans-Monfort, Xavier, Salaverri Mora, Noelia, Marzo Puerta, Leyre, Mas Ballesté, Rubén, Alemán Lara, José Julián
Formato: artículo
Fecha de publicación:2023
País:España
Recursos:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/709576
Acesso em linha:http://hdl.handle.net/10486/709576
https://dx.doi.org/10.1002/solr.202300768
Access Level:acceso abierto
Palavra-chave:Covalent Organic Frameworks
Covalent Triazine Frameworks
Energy Transfer
Photocatalysis
Photoredox
Química
Descrição
Resumo:Two organic materials containing phenanthroline and triazine fragments, but connected in different ways, are presented. The imine-based material Phen–Tz–covalent organic framework (COF) preferentially shows photocatalytic activity through an energy transfer pathway as observed for olefin photoisomerization. However, an analogous covalent triazine framework (Phen–CTF) behaves as a powerful photoredox catalyst able to activate C-X (X=Br, Cl) bonds. The analysis of this phenomenon by means of theoretical calculations enables the rationalization of the different photocatalytic behavior observed. Phen–CTF behaves as a donor–acceptor material resulting in efficient charge separation upon excitation, while the imine groups present in Phen–Tz–COF hamper charge separation contributing to the rapid recombination between electrons and holes. This justifies a better activation via electron transfer in Phen–CTF and via energy transfer in Phen–Tz–COF