title: Synchronized Offset Stacking: A Concept for Growing Large-Domain and Highly Crystalline 2D Covalent Organic Frameworks.
abstract: Covalent organic frameworks (COFs), formed by reversible condensation of rigid organic building blocks, are crystalline and porous materials of great potential for catalysis and organic electronics. Particularly with a view of organic electronics, achieving a maximum degree of crystallinity and large domain sizes while allowing for a tightly π-stacked topology would be highly desirable. We present a design concept that uses the 3D geometry of the building blocks to generate a lattice of uniquely defined docking sites for the attachment of consecutive layers, thus allowing us to achieve a greatly improved degree of order within a given average number of attachment and detachment cycles during COF growth. Synchronization of the molecular geometry across several hundred nanometers promotes the growth of highly crystalline frameworks with unprecedented domain sizes. Spectroscopic data indicate considerable delocalization of excitations along the π-stacked columns and the feasibility of donor-acceptor excitations across the imine bonds. The frameworks developed in this study can serve as a blueprint for the design of a broad range of tailor-made 2D COFs with extended π-conjugated building blocks for applications in photocatalysis and optoelectronics.
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.|Cavendish Laboratory, University of Cambridge , Cambridge CB3 0HE, United Kingdom.
authors.forename: Florian
authors.identifier: 0000-0003-1709-4384
authors.initials: F
authors.lastname: Auras
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.
authors.forename: Laura
authors.initials: L
authors.lastname: Ascherl
authors.affiliation: Friedrich-Alexander-University Erlangen-Nürnberg (FAU) , Computer-Chemie-Centrum, Nägelsbachstraße 25, 91052 Erlangen, Germany.
authors.forename: Amir H
authors.initials: AH
authors.lastname: Hakimioun
authors.affiliation: Friedrich-Alexander-University Erlangen-Nürnberg (FAU) , Computer-Chemie-Centrum, Nägelsbachstraße 25, 91052 Erlangen, Germany.
authors.forename: Johannes T
authors.initials: JT
authors.lastname: Margraf
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.
authors.forename: Fabian C
authors.initials: FC
authors.lastname: Hanusch
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.
authors.forename: Stephan
authors.initials: S
authors.lastname: Reuter
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.
authors.forename: Derya
authors.initials: D
authors.lastname: Bessinger
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.
authors.forename: Markus
authors.initials: M
authors.lastname: Döblinger
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.
authors.forename: Christina
authors.initials: C
authors.lastname: Hettstedt
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.
authors.forename: Konstantin
authors.initials: K
authors.lastname: Karaghiosoff
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.
authors.forename: Simon
authors.initials: S
authors.lastname: Herbert
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.
authors.forename: Paul
authors.identifier: 0000-0001-8167-272X
authors.initials: P
authors.lastname: Knochel
authors.affiliation: Friedrich-Alexander-University Erlangen-Nürnberg (FAU) , Computer-Chemie-Centrum, Nägelsbachstraße 25, 91052 Erlangen, Germany.
authors.forename: Timothy
authors.identifier: 0000-0001-7931-4659
authors.initials: T
authors.lastname: Clark
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, 81377 Munich, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Bein