Porphyrin hexamer with a triphenylene core unit: Spectroscopy, electrochemistry and controllable supramolecular formation

Abstract

A series of free-base and zinc porphyrin hexamers, where six porphyrin units are linked to a triphenylene core through amide or ester linkage, was designed and synthesized in an effort to study their spectroscopic and electrochemical properties, and aggregate formation. The distances between triphenylene core and porphyrin moieties are tuned by changing the lengths of spacer alkyl chains. The absorption spectral studies indicates that the porphyrin units in a hexamer behave like monomeric porphyrins, while a strong fluorescence quenching of triphenylene core was observed suggesting the deactivation of the excited state of triphenylene. The redox potentials of porphyrin units in a hexamer were estimated by differential pulse voltammetry (DPV). These values are very similar to those of the corresponding monomer. Consequently, absorption and electrochemical data demonstrate that six porphyrin units of (H2PAC5)6TPh behave like monomers independently in the ground state. The hexamers undergo supramolecular aggregation spontaneously in different fashions based on the solvent systems as well as spacer lengths. Highly ordered and aligned monolayer-based patterns are formed when hexamers are allowed to aggregate from toluene solution onto carbon-coated copper films. In contrast, hexamers undergo aggregation to nanoparticles in toluene/acetonitrile mixed solvent system and the particle sizes increase with increasing the spacer alkyl chain lengths.