Efficient Excited-State Symmetry Breaking in a Cationic Quadrupolar System Bearing Diphenylamino Donors

Benedetta Carlotti, Enrico Benassi, Cosimo G. Fortuna, Vincenzo Barone, Anna Spalletti, Fausto Elisei

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

We report a joint experimental and theoretical investigation of a quadrupolar D-π-A+-π-D system, the electron donors being diphenylamino groups and the electron acceptor being a methylpyridinium, in comparison with the dipolar D-π-A+ system. The emission spectra of the two compounds overlap in all the investigated solvents. This finding could be rationalized by TD-DFT calculations: the LUMO-HOMO molecular orbitals involved in the emission transition are localized on the same branch of the quadrupolar structure that becomes the fluorescent portion, corresponding to that of the single-arm compound. Excited-state symmetry breaking has been rarely observed for quadrupolar systems showing negative solvatochromism and is here surprisingly revealed, even in low polarity solvents. Femtosecond transient absorption measurements revealed that an efficient photoinduced intramolecular charge transfer takes place in the quadrupolar chromophore, more efficient than in its dipolar analogue. This result is promising in view of the application of these compounds as novel two-photon absorbing materials. The emission spectra of a quadrupolar compound and its dipolar analogue overlap in all the investigated solvents, regardless of their polarity. Excited-state symmetry breaking, which is rarely observed in quadrupolar systems showing negative solvatochromism, is revealed. The results are promising for the development of novel two-photon absorbing materials.

Original languageEnglish
Pages (from-to)136-146
Number of pages11
JournalChemPhysChem
Volume17
Issue number1
DOIs
Publication statusPublished - 4 Jan 2016
Externally publishedYes

Fingerprint

Bearings (structural)
Crystal symmetry
Excited states
broken symmetry
polarity
emission spectra
Photons
analogs
excitation
Electrons
photons
Molecular orbitals
Chromophores
Discrete Fourier transforms
chromophores
Charge transfer
molecular orbitals
electrons
charge transfer

Keywords

  • femtosecond transient absorption
  • intramolecular charge transfer
  • quadrupolar systems
  • solvent effects
  • TD-DFT calculations

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

Cite this

Efficient Excited-State Symmetry Breaking in a Cationic Quadrupolar System Bearing Diphenylamino Donors. / Carlotti, Benedetta; Benassi, Enrico; Fortuna, Cosimo G.; Barone, Vincenzo; Spalletti, Anna; Elisei, Fausto.

In: ChemPhysChem, Vol. 17, No. 1, 04.01.2016, p. 136-146.

Research output: Contribution to journalArticle

Carlotti, Benedetta ; Benassi, Enrico ; Fortuna, Cosimo G. ; Barone, Vincenzo ; Spalletti, Anna ; Elisei, Fausto. / Efficient Excited-State Symmetry Breaking in a Cationic Quadrupolar System Bearing Diphenylamino Donors. In: ChemPhysChem. 2016 ; Vol. 17, No. 1. pp. 136-146.
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