Owing to the attractive potential applications of porphyrin assemblies in photocatalysis, sensors, and material science, studies presently concerning porphyrin aggregation are widely diffused. pi-pi 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-pi 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.

Sabuzi, F., Stefanelli, M., Monti, D., Conte, V., & Galloni, P. (2019). Amphiphilic porphyrin aggregates: A DFT investigation. MOLECULES, 25(1), 133 [10.3390/molecules25010133].

Amphiphilic porphyrin aggregates: A DFT investigation

Sabuzi F.
;
Stefanelli M.;Monti D.;Conte V.;Galloni P.
2019

Abstract

Owing to the attractive potential applications of porphyrin assemblies in photocatalysis, sensors, and material science, studies presently concerning porphyrin aggregation are widely diffused. pi-pi 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-pi 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.
Pubblicato
Rilevanza internazionale
Articolo
Sì, ma tipo non specificato
Settore CHIM/06
English
DFT calculations; H-type dimer; aggregation; cation–π dimer; porphyrin dimers
Sabuzi, F., Stefanelli, M., Monti, D., Conte, V., & Galloni, P. (2019). Amphiphilic porphyrin aggregates: A DFT investigation. MOLECULES, 25(1), 133 [10.3390/molecules25010133].
Sabuzi, F; Stefanelli, M; Monti, D; Conte, V; Galloni, P
Articolo su rivista
File in questo prodotto:
File Dimensione Formato  
molecules-25-00133.pdf

accesso aperto

Licenza: Copyright dell'editore
Dimensione 4.73 MB
Formato Adobe PDF
4.73 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/242482
Citazioni
  • ???jsp.display-item.citation.pmc??? 1
  • Scopus 4
  • ???jsp.display-item.citation.isi??? 7
social impact