Single Crystals of Perylene Diimide‐Based Two‐Dimensional Covalent Organic Frameworks
Abstract
ABSTRACT Two‐dimensional covalent organic frameworks (2D COFs) are crystalline porous polymers with highly tunable structural and electronic properties. Although single crystals of these materials are highly desirable for fundamental research and potential applications, their synthesis has so far been limited to only a few examples. We have developed a high‐temperature double‐modulator synthetic strategy that enables the growth of single crystals from fully dissolved precursors. We applied this approach to generate a series of perylene diimide (PDI)‐based 2D COFs. These materials crystallize as platelets with lateral dimensions reaching up to 50 µm for the biphenyl‐linked PDI(Me) 8 ‐2P COF, providing a suitable platform for studying electronic processes via micro‐spectroscopy. Photoluminescence (PL) measurements revealed ultrafast monomer‐like emission together with a slower excimer‐related component. The availability of COF single crystals further enabled polarization‐dependent measurements, which revealed that the fast PL component is linearly polarized due to the parallel orientation of the PDI chromophores in the frameworks. These findings highlight the importance of COF single crystals for elucidating structure—photophysical property relationships of these intriguing materials.
Article Details
Authors (13)
Ling Zhang
Zixuan Chen
State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry, School of Environment
Lukas Mühlnickel
Institute of Applied Physics and Würzburg‐Dresden Cluster of Excellence ctd.qmat TUD Dresden University of Technology Dresden Germany
Lukas Sporrer
Jakub D. Jasinski
Institute of Applied Physics and Würzburg‐Dresden Cluster of Excellence ctd.qmat TUD Dresden University of Technology Dresden Germany
Megha Koottungal
Faculty of Chemistry and Food Chemistry TUD Dresden University of Technology Dresden Germany
Kevin Synnatschke
Chair for Molecular Functional Materials, TU Dresden, Stadtgutstr. 59, 01217 Dresden, Germany
Paul‐Felix Jordan
Faculty of Chemistry and Food Chemistry TUD Dresden University of Technology Dresden Germany
Silvia Paasch
Faculty of Chemistry and Food Chemistry TUD Dresden University of Technology Dresden Germany
Eike Brunner
Chair of Bioanalytical Chemistry
Zhehao Huang
Department of Chemistry
Alexey Chernikov
Florian Auras
Cavendish Laboratory, Department of Physics