Entanglement of Square Nets in Covalent Organic Frameworks

Two entangled 2D square 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 propencity of 2D COFs to stack through π-π stacking and allows for entanglements to form. This work adds significantly to the design principles of COFs.