title: Conjugated Covalent Organic Frameworks via Michael Addition-Elimination.
abstract: Dynamic covalent chemistry enables self-assembly of reactive building blocks into structurally complex yet robust materials, such as covalent organic frameworks (COFs). However, the synthetic toolbox used to prepare such materials, and thus the spectrum of attainable properties, is very limited. For π-conjugated COFs, the Schiff base condensation of aldehydes and amines is the only general dynamic reaction, but the resulting imine-linked COFs display only a moderate electron delocalization and are susceptible to hydrolysis, particularly in acidic conditions. Here we report a new dynamic polymerization based on Michael addition-elimination reaction of structurally diverse β-ketoenols with amines, and use it to prepare novel two-dimensional (2D) π-conjugated COFs, as crystalline powders and exfoliated micron-size sheets. π-Conjugation is manifested in these COFs in significantly reduced band gap (1.8-2.2 eV), solid state luminescence and reversible electrochemical doping creating midgap (NIR absorbing) polaronic states. The β-ketoenamine moiety enables protonation control of electron delocalization through the 2D COF sheets. It also gives rise to direct sensing of triacetone triperoxide (TATP) explosive through fluorescence quenching.
authors.affiliation: Department of Chemistry, McGill University , 801 Sherbrooke Street West, Montreal, Quebec H3A 0B8, Canada.
authors.forename: M Rajeswara
authors.initials: MR
authors.lastname: Rao
authors.affiliation: Department of Chemistry, McGill University , 801 Sherbrooke Street West, Montreal, Quebec H3A 0B8, Canada.|Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven - University of Leuven , Celestijnenlaan 200 F, B-3001 Leuven, Belgium.
authors.forename: Yuan
authors.initials: Y
authors.lastname: Fang
authors.affiliation: Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven - University of Leuven , Celestijnenlaan 200 F, B-3001 Leuven, Belgium.
authors.forename: Steven
authors.initials: S
authors.lastname: De Feyter
authors.affiliation: Department of Chemistry, McGill University , 801 Sherbrooke Street West, Montreal, Quebec H3A 0B8, Canada.
authors.forename: Dmitrii F
authors.identifier: 0000-0003-2233-416X
authors.initials: DF
authors.lastname: Perepichka