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

• Published in: Chemphyschem Vol. 17; no. 1; pp. 136 - 146
• Main Authors: Carlotti, Benedetta, Benassi, Enrico, Fortuna, Cosimo G., Barone, Vincenzo, Spalletti, Anna, Elisei, Fausto
• Format: Journal Article
• Language: English
• Published: Germany Blackwell Publishing Ltd 04.01.2016; Wiley Subscription Services, Inc
• Subjects: Diphenylamine - analogs & derivatives; Diphenylamine - chemistry; femtosecond transient absorption; Fluorescence; intramolecular charge transfer; Models, Chemical; Pyridinium Compounds - chemistry; quadrupolar systems; solvent effects; Solvents; Spectrum Analysis; TD-DFT calculations; solvent effects; femtosecond transient absorption; intramolecular charge transfer; quadrupolar systems; TD-DFT calculations
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.201500784

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.