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 pi-pi stacking and allows entanglements to form. This work significantly adds to the design principles of COFs.
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