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Thermodynamic Self Assembly of Two-Dimensional pi-Conjugated Metal-Porphyrin Covalent Organic Frameworks by On-Site Equilibrium Polymerization

Two dimensional pi conjugated metal porphyrin covalent organic frameworks were produced in aqueous solution on an iodine-modified Au(111) surface by on site azomethine coupling of Fe(III) 5,10,15,20 tetrakis(4 aminophenyl)porphyrin (FeTAPP) with terephthal dicarboxaldehyde and investigated in detail using in-situ scanning tunneling microscopy. Mixed covalent organic porphyrin frameworks consisting of FeTAPP and metal-free TAPP (H2TAPP) were prepared through simultaneous adsorption in a mixed solution as well as partial replacement of FeTAPP by H2TAPP in an as prepared metal porphyrin framework. In the mixed framework, the relative distribution of FeTAPP to H2TAPP was not random and revealed a preference for homo-connection rather than heteroconnection. The construction of substrate-supported, pi conjugated covalent frameworks from multiple building blocks, including metal centers, will be of significant utility in the design of functional molecular nanoarchitectures.