Modular Synthesis of trans-A2 B2 -Porphyrins with Terminal Esters: Systematically Extending the Scope of Linear Linkers for Porphyrin-Based MOFs

Chemistry. 2021 Jan 18;27(4):1390-1401. doi: 10.1002/chem.202003885. Epub 2020 Dec 10.

Abstract

Differently functionalized porphyrin linkers represent the key compounds for the syntheses of new porphyrin-based metal-organic frameworks (MOFs), which have gathered great interest within the last two decades. Herein we report the synthesis of a large range of 5,15-bis(4-ethoxycarbonylphenyl)porphyrin derivatives, through Suzuki and Sonogashira cross-coupling reactions of an easily accessible corresponding meso-dibrominated trans-A2 B2 -porphyrin with commercially available boronic acids or terminal alkynes. The resulting porphyrins were fully characterized through NMR, MS, and IR spectroscopy and systematically investigated through UV/Vis absorption. Finally, selected structures were saponified to the corresponding carboxylic acids and subsequently proven to be suitable for the synthesis of surface-anchored MOF thin films.

Keywords: heterocycles; metal-organic frameworks; nitrogen heterocycles; porphyrinoids; thin films.