Synchronized Offset Stacking: A Concept for Growing Large-Domain and Highly Crystalline 2D Covalent Organic Frameworks

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• 作者：Florian AurasLaura Ascherl ; Amir H. Hakimioun ; Johannes T. Margraf ; Fabian C. Hanusch ; Stephan Reuter ; Derya Bessinger ; Markus Döblinger ; Christina Hettstedt ; Konstantin Karaghiosoff ; Simon Herbert ; Paul Knochel ; Timothy ClarkThomas Bein
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：December 28, 2016
• 年：2016
• 卷：138
• 期：51
• 页码：16703-16710
• 全文大小：626K
• ISSN：1520-5126

文摘

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.