Spectral properties and photobehaviour of 2,5-distyrylfuran derivatives

Ciorba, Serena; Carlotti, Benedetta; Škorić, Irena; Šindler‐Kulyk, Marija; Spalletti, Anna

doi:10.1016/j.jphotochem.2011.01.009

Cited by 22 publications

(28 citation statements)

References 20 publications

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“…[3][4][5][6][7][8][9] It has been observed that the extent of the NLO response and the two photon absorption cross-sections are strongly dependent upon the molecular structure of the pushpull molecules and are particularly affected by the strengths of the electron donor/acceptor groups. [14][15][16][17][18] This effect was observed not only in widely studied neutral donor-acceptor systems, but also in cationic chromophores bearing a methyl pyridinium or a methyl quinolinium as an electron deficient moiety, [19][20][21][22][23][24] whose photobehaviour has been less investigated so far and, therefore, not yet deeply understood. [14][15][16][17][18] This effect was observed not only in widely studied neutral donor-acceptor systems, but also in cationic chromophores bearing a methyl pyridinium or a methyl quinolinium as an electron deficient moiety, [19][20][21][22][23][24] whose photobehaviour has been less investigated so far and, therefore, not yet deeply understood.…”

Section: Introductionmentioning

confidence: 99%

An ultrafast spectroscopic and quantum mechanical investigation of multiple emissions in push–pull pyridinium derivatives bearing different electron donors

Carlotti

Benassi

Cesaretti

et al. 2015

Phys. Chem. Chem. Phys.

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A joint experimental and theoretical approach, involving state-of-the-art femtosecond fluorescence up-conversion measurements and quantum mechanical computations including vibronic effects, was employed to get a deep insight into the excited state dynamics of two cationic dipolar chromophores (Donor-π-Acceptor(+)) where the electron deficient portion is a N-methyl pyridinium and the electron donor a trimethoxyphenyl or a pyrene, respectively. The ultrafast spectroscopic investigation, and the time resolved area normalised emission spectra in particular, revealed a peculiar multiple emissive behaviour and allowed the distinct emitting states to be remarkably distinguished from solvation dynamics, occurring in water in a similar timescale. The two and three emissions experimentally detected for the trimethoxyphenyl and pyrene derivatives, respectively, were associated with specific local emissive minima in the potential energy surface of S1 on the ground of quantum-mechanical calculations. A low polar and planar Locally Excited (LE) state together with a highly polar and Twisted Intramolecular Charge Transfer (TICT) state is identified to be responsible for the dual emission of the trimethoxyphenyl compound. Interestingly, the more complex photobehaviour of the pyrenyl derivative was explained considering the contribution to the fluorescence coming not only from the LE and TICT states but also from a nearly Planar Intramolecular Charge Transfer (PICT) state, with both the TICT and the PICT generated from LE by progressive torsion around the quasi-single bond between the methylpyridinium and the ethene bridge. These findings point to an interconversion between rotamers for the pyrene compound taking place in its excited state against the Non-equilibrated Excited Rotamers (NEER) principle.

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Section: Introductionmentioning

confidence: 99%

An ultrafast spectroscopic and quantum mechanical investigation of multiple emissions in push–pull pyridinium derivatives bearing different electron donors

Carlotti

Benassi

Cesaretti

et al. 2015

Phys. Chem. Chem. Phys.

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“…The excited state relaxation yields of the compounds with a central furan group do not show important changes with respect to the unsubstituted [17] and mono(nitro)-substituted [4] analogues previously investigated (high emission and quite low isomerization yields). The sizable decrease of fluorescence and increase of reactivity of the thiophene compared to the furan derivatives, previously reported and probably due to ISC induced by the sulphur heteroatom [15], was here maintained for the methoxy-substituted NODST only, whereas the dimethylamino-substituted NNDST displays a behaviour similar to the furan analogue.…”

Section: Photobehaviourmentioning

confidence: 64%

“…The NNDSP is poorly fluorescent, while its methoxy analogue does not emit at all. Comparison of the spectral properties of these push-pull systems bearing electron donor/acceptor groups with the unsubstituted (Table 1) and monosubstituted [4] analogues shows a significant red shift, reasonably assignable to the CT character of the first transitions (see below).…”

Section: Spectral Propertiesmentioning

confidence: 90%

“…We reported recently the synthesis and photophysical study of conjugated systems bearing electron-donor/acceptor groups at the extreme ends, connected by a spacer [1][2][3][4][5][6][7]. The design and study of these push-pull (D--A) systems have attracted our attention because of their potential application as fluorescent probes, as dye laser systems and in optoelectronics [8,9], especially for their hyperpolarizability properties which make them candidates as components of non linear optical (NLO) materials [10][11][12][13].…”

Section: Introductionmentioning

confidence: 99%

“…Of particular interest was the study of 2-(p-nitrostyryl),5-styrylfuran and 2-(p-methylstyryl),3-(p-nitrostyryl)benzofuran [1,2,4,5], where the nitro group and the central -excessive furan ring are responsible for the introduction of electronic states with a strong CT character. Moreover, in the first molecule a peculiar, very interesting, dependence of the intersystem crossing kinetic constant (k ISC ) on the dielectric constant (ε) of the solvent was evidenced [14].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis, spectral properties and photobehaviour of push–pull distyrylbenzene nitro-derivatives

Kikaš

Carlotti

Škorić

et al. 2012

Journal of Photochemistry and Photobiology A: Chemistry

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Comprehensive Photophysical Behaviour of Ethynyl Fluorenes and Ethynyl Anthracenes Investigated by Fast and Ultrafast Time‐Resolved Spectroscopy

et al. 2012

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Detailed investigations by time-resolved transient absorption and fluorescence spectroscopies with nano- and femtosecond time resolutions are carried out with the aim of characterising the lowest excited singlet and triplet states of three ethynyl fluorenes (1-3) and three ethynyl anthracenes (4-6) in solvents of different polarity. The solvent is found to modify the deactivation pathways of the lowest excited singlet state of compounds 1-4, thus changing their fluorescence, intersystem crossing and internal conversion efficiencies. The fluorescence and triplet yields gradually decrease, while the internal conversion quantum yield increases upon increasing the solvent dielectric constant. These experimental results, coupled with the marked fluorosolvatochromic effect, point to the involvement of an emitting state with a charge-transfer (CT) character, strongly stabilised by polar solvents. This is proved by ultrafast spectroscopic studies in which two transients, distinguished by characteristic spectral shapes assigned to locally excited (LE) and CT states, are detected, the CT state being the longer lived and fluorescent one in highly polar solvents. The intramolecular LE→CT process, operative in highly polar media, becomes particularly fast (up to ≈300 fs) in the case of the NO(2) derivative 1. No push-pull character is found for 5 and 6, which exhibit different photophysical behaviour; indeed, the solvent polarity does not modify significantly the dynamics of the lowest excited singlet states. Quantum mechanical calculations at the TDDFT level are also used to determine the state order and nature of the lowest excited singlet and triplet states and to rationalise the different photophysical behaviour of fluorine and anthracene derivatives, particularly concerning the intersystem crossing process.

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Spectral properties and photobehaviour of 2,5-distyrylfuran derivatives

Cited by 22 publications

References 20 publications

An ultrafast spectroscopic and quantum mechanical investigation of multiple emissions in push–pull pyridinium derivatives bearing different electron donors

An ultrafast spectroscopic and quantum mechanical investigation of multiple emissions in push–pull pyridinium derivatives bearing different electron donors

Synthesis, spectral properties and photobehaviour of push–pull distyrylbenzene nitro-derivatives

Comprehensive Photophysical Behaviour of Ethynyl Fluorenes and Ethynyl Anthracenes Investigated by Fast and Ultrafast Time‐Resolved Spectroscopy

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