Three new perylenetetracarboxy-3,4:9,10-diimides, bearing 2,6-diisopropylphenyl groups at the imide positions and 4-(R-ethynyl)phenoxy moieties (R = 4,7-di(2-thienyl)benzo[c][1,2,5]thiadiazole (P2), pyrene (P3) or pyrene-CH2OCH2 (P4)) at the four bay positions, were prepared, along with the known related derivative (R = phenyl (P1)), and well characterized. They have large two-photon absorption (TPA) cross-sections (sigma(2)), as determined by the Z-scan technique, the highest values being reached with P2 which bears a planar -delocalized donor moiety. P3 is characterized by higher sigma(2) values than both P1, as expected for the higher -conjugation of the donor pyrene moiety with respect to phenyl, and P4, due to the presence of the flexible and non-conjugated CH2OCH2 bridge between the pyrene and the ethynyl fragment in the latter compound. The molecular geometry of P1-P4 has been optimized by DFT modeling, showing that in P2 and P3 the bay substituents are stacked due to the - interactions of both pyrene and thiophene groups. The LUMO of P1-P4 lies at the same energy and is essentially delocalized on the perylene core whereas the HOMO and HOMO-1 of both P2 and P3 are degenerate and do not show contribution from the perylene core contrarily to that of P1 and P4. The HOMO-LUMO gap is therefore essentially influenced by the HOMO which reflects the electronic charge delocalization on the bay substituents, the lower gaps being observed for P2 and P3, which are characterized by the best TPA properties.

Perylenetetracarboxy-3,4:9,10-diimide derivatives with large two-photon absorption activity / E. Garoni, F. Nisic, A. Colombo, S. Fantacci, G. Griffini, K. Kamada, D. Roberto, C. Dragonetti. - In: NEW JOURNAL OF CHEMISTRY. - ISSN 1144-0546. - 43:4(2019 Jan 28), pp. 1885-1893. [10.1039/C8NJ03216E]

Perylenetetracarboxy-3,4:9,10-diimide derivatives with large two-photon absorption activity

E. Garoni
Primo
;
F. Nisic
Secondo
;
A. Colombo
;
D. Roberto
Penultimo
;
C. Dragonetti
Ultimo
2019-01-28

Abstract

Three new perylenetetracarboxy-3,4:9,10-diimides, bearing 2,6-diisopropylphenyl groups at the imide positions and 4-(R-ethynyl)phenoxy moieties (R = 4,7-di(2-thienyl)benzo[c][1,2,5]thiadiazole (P2), pyrene (P3) or pyrene-CH2OCH2 (P4)) at the four bay positions, were prepared, along with the known related derivative (R = phenyl (P1)), and well characterized. They have large two-photon absorption (TPA) cross-sections (sigma(2)), as determined by the Z-scan technique, the highest values being reached with P2 which bears a planar -delocalized donor moiety. P3 is characterized by higher sigma(2) values than both P1, as expected for the higher -conjugation of the donor pyrene moiety with respect to phenyl, and P4, due to the presence of the flexible and non-conjugated CH2OCH2 bridge between the pyrene and the ethynyl fragment in the latter compound. The molecular geometry of P1-P4 has been optimized by DFT modeling, showing that in P2 and P3 the bay substituents are stacked due to the - interactions of both pyrene and thiophene groups. The LUMO of P1-P4 lies at the same energy and is essentially delocalized on the perylene core whereas the HOMO and HOMO-1 of both P2 and P3 are degenerate and do not show contribution from the perylene core contrarily to that of P1 and P4. The HOMO-LUMO gap is therefore essentially influenced by the HOMO which reflects the electronic charge delocalization on the bay substituents, the lower gaps being observed for P2 and P3, which are characterized by the best TPA properties.
Settore CHIM/03 - Chimica Generale e Inorganica
Article (author)
File in questo prodotto:
File Dimensione Formato  
New J of Chem. 2019 asap per AIR.pdf

embargo fino al 11/03/2020

Tipologia: Post-print, accepted manuscript ecc. (versione accettata dall'editore)
Dimensione 722.89 kB
Formato Adobe PDF
722.89 kB Adobe PDF Visualizza/Apri
71.New J. Chem., 2019.pdf

accesso riservato

Tipologia: Publisher's version/PDF
Dimensione 2.48 MB
Formato Adobe PDF
2.48 MB Adobe PDF   Visualizza/Apri   Richiedi una copia
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

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: http://hdl.handle.net/2434/614095
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 5
  • ???jsp.display-item.citation.isi??? 5
social impact