Entanglement of Square Nets in Covalent Organic Frameworks
Fangying Jin1, Ha L Nguyen1,2, Zhiye Zhong3
1Department of Chemistry, University of California-Berkeley, Kavli Energy Nanoscience Institute at UC Berkeley, and Berkeley Global Science Institute, Berkeley, California 94720, United States.
Abstract:
Two entangled 2D square covalent organic frameworks (COFs) have been synthesized from 4,4',4″,4‴-(9,9'-spirobi[fluorene]-2,2',7,7'-tetrayl)-tetrabenzaldehhyde (SFTB) and p-phenylenediamine (PPA) and benzidine (BZD) to form COF-38, [(SFTB)(PPA)2]imine, and its isoreticular form COF-39, [(SFTB)(BZD)2]imine. We also report the single-crystal electron diffraction structure of COF-39 and find that it is composed of mutually entangled 2D square nets (sql). These COFs represent the first examples of entangled 2D COF structures, which, as we illustrate, were made possible by our strategy of using the distorted tetrahedral SFTB building unit. SFTB overcomes the propensity of 2D COFs to stack through π-π stacking and allows entanglements to form. This work significantly adds to the design principles of COFs.
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