A Strongly Reducing sp2 Carbon-Conjugated Covalent Organic Framework Formed by N-Heterocyclic Carbene Dimerization.
Angew Chem Int Ed Engl
; : e202416480, 2024 Sep 15.
Article
em En
| MEDLINE
| ID: mdl-39278822
ABSTRACT
Covalent organic frameworks linked by carbon-carbon double bonds (C=C COFs) are an emerging class of crystalline, porous, and conjugated polymeric materials with potential applications in organic electronics, photocatalysis, and energy storage. Despite the rapidly growing interest in sp2 carbon-conjugated COFs, only a small number of closely related condensation reactions have been successfully employed for their synthesis to date. Herein, we report the first example of a C=C COF, CORN-COF-1 (CORN = Cornell University), prepared by N-heterocyclic carbene (NHC) dimerization. In-depth characterization reveals that CORN-COF-1 possesses a two-dimensional layered structure and hexagonal guest-accessible pores decorated with a high density of strongly reducing tetraazafulvalene linkages. Exposure of CORN-COF-1 to tetracyanoethylene (TCNE, E1/2 = 0.13 V and -0.87 V vs. SCE) oxidizes the COF and encapsulates the radical anion TCNEâ¢- and the dianion TCNE2- as guest molecules, as confirmed by spectroscopic and magnetic analysis. Notably, the reactive TCNEâ¢- radical anion, which generally dimerizes in the solid state, is uniquely stabilized within the pores of CORN-COF-1. Overall, our findings broaden the toolbox of reactions available for the synthesis of redox-active C=C COFs, paving the way for the design of novel materials.
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1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Estados Unidos