Amphiphilic Porphyrin Aggregates: A DFT Investigation

Molecules

Valeria Conte¹  Donato Monti¹  Pierluca Galloni¹  Federica Sabuzi¹  Manuela Stefanelli¹ 

[1] Department of Chemical Sciences and Technologies, University of Rome Tor Vergata, Via della Ricerca Scientifica snc, 00133 Rome, Italy;

关键词: dft calculations;    aggregation;    porphyrin dimers;    cation–π dimer;    h-type dimer;   

DOI  :  10.3390/molecules25010133

来源: DOAJ

【 摘 要 】

Owing to the attractive potential applications of porphyrin assemblies in photocatalysis, sensors, and material science, studies presently concerning porphyrin aggregation are widely diffused. π−π stacking, H-bonding, metal coordination, hydrophobic effect, and electrostatic forces usually drive porphyrin interaction in solution. However, theoretical studies of such phenomena are still limited. Therefore, a computational examination of the different porphyrin aggregation approaches is proposed here, taking into account amphiphilic [5-{4-(3-trimethylammonium)propyloxyphenyl}-10,15,20-triphenylporphyrin] chloride, whose aggregation behavior has been previously experimentally investigated. Different functionals have been adopted to investigate the porphyrin dimeric species, considering long-range interactions. Geometry optimization has been performed, showing that for the compound under analysis, H-type and cation−π dimers are the most favored structures that likely co-exist in aqueous solution. Of note, frontier orbital delocalization showed an interesting interaction between the porphyrin units in the dimer at the supramolecular level.

【 授权许可】

Unknown