title: Thermodynamic self-assembly of two-dimensional pi-conjugated metal-porphyrin covalent organic frameworks by "on-site" equilibrium polymerization.
abstract: 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.
authors.forename: Ryota
authors.initials: R
authors.lastname: Tanoue
authors.forename: Rintaro
authors.initials: R
authors.lastname: Higuchi
authors.forename: Kiryu
authors.initials: K
authors.lastname: Ikebe
authors.forename: Shinobu
authors.initials: S
authors.lastname: Uemura
authors.forename: Nobuo
authors.initials: N
authors.lastname: Kimizuka
authors.forename: Adam Z
authors.initials: AZ
authors.lastname: Stieg
authors.forename: James K
authors.initials: JK
authors.lastname: Gimzewski
authors.forename: Masashi
authors.initials: M
authors.lastname: Kunitake