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Experimental and Theoretical Studies of Quadrupolar Oligothiophene-Cored Chromophores Containing Dimesitylboryl Moieties as π-Accepting End-Groups: Syntheses, Structures, Fluorescence, and One- and Two-Photon Absorption

Ji, L.; Edkins, R.M.; Sewell, L.J.; Beeby, A.; Batsanov, A.S; Fucke, K.; Drafz, M.; Howard, J.A.K.; Moutounet, O.; Ibersiene, F.; Boucekkine, A.; Furet, E.; Liu, Z.; Halet, J.F.; Katan, C.; Marder, T.B.

Experimental and Theoretical Studies of Quadrupolar Oligothiophene-Cored Chromophores Containing Dimesitylboryl Moieties as π-Accepting End-Groups: Syntheses, Structures, Fluorescence, and One- and Two-Photon Absorption Thumbnail


Authors

L. Ji

R.M. Edkins

L.J. Sewell

A.S Batsanov

K. Fucke

M. Drafz

J.A.K. Howard

O. Moutounet

F. Ibersiene

A. Boucekkine

E. Furet

Z. Liu

J.F. Halet

C. Katan

T.B. Marder



Abstract

Quadrupolar oligothiophene chromophores composed of four to five thiophene rings with two terminal (E)-dimesitylborylvinyl groups (4 V–5 V), and five thiophene rings with two terminal aryldimesitylboryl groups (5 B), as well as an analogue of 5 V with a central EDOT ring (5 VE), have been synthesized via Pd-catalyzed cross-coupling reactions in high yields (66–89 %). Crystal structures of 4 V, 5 B, bithiophene 2 V, and five thiophene-derived intermediates are reported. Chromophores 4 V, 5 V, 5 B and 5 VE have photoluminescence quantum yields of 0.26–0.29, which are higher than those of the shorter analogues 1 V–3 V (0.01–0.20), and short fluorescence lifetimes (0.50–1.05 ns). Two-photon absorption (TPA) spectra have been measured for 2 V–5 V, 5 B and 5 VE in the range 750–920 nm. The measured TPA cross-sections for the series 2 V–5 V increase steadily with length up to a maximum of 1930 GM. We compare the TPA properties of 2 V–5 V with the related compounds 5 B and 5 VE, giving insight into the structure–property relationship for this class of chromophore. DFT and TD-DFT results, including calculated TPA spectra, complement the experimental findings and contribute to their interpretation. A comparison to other related thiophene and dimesitylboryl compounds indicates that our design strategy is promising for the synthesis of efficient dyes for two-photon-excited fluorescence applications.

Citation

Ji, L., Edkins, R., Sewell, L., Beeby, A., Batsanov, A., Fucke, K., …Marder, T. (2014). Experimental and Theoretical Studies of Quadrupolar Oligothiophene-Cored Chromophores Containing Dimesitylboryl Moieties as π-Accepting End-Groups: Syntheses, Structures, Fluorescence, and One- and Two-Photon Absorption. Chemistry - A European Journal, 20(42), 13618-13635. https://doi.org/10.1002/chem.201402273

Journal Article Type Article
Publication Date Oct 13, 2014
Deposit Date Sep 2, 2014
Publicly Available Date Sep 5, 2014
Journal Chemistry - A European Journal
Print ISSN 0947-6539
Electronic ISSN 1521-3765
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 20
Issue 42
Pages 13618-13635
DOI https://doi.org/10.1002/chem.201402273
Keywords Boron, Density functional calculations, Luminescence, Nonlinear optics, Photophysics.

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Copyright Statement
This is the peer reviewed version of the following article: Ji, L., Edkins, R. M., Sewell, L. J., Beeby, A., Batsanov, A. S., Fucke, K., Drafz, M., Howard, J. A. K., Moutounet, O., Ibersiene, F., Boucekkine, A., Furet, E., Liu, Z., Halet, J.-F., Katan, C. and Marder, T. B. (2014), Experimental and Theoretical Studies of Quadrupolar Oligothiophene-Cored Chromophores Containing Dimesitylboryl Moieties as π-Accepting End-Groups: Syntheses, Structures, Fluorescence, and One- and Two-Photon Absorption. Chemistry - a European journal, 20 (42): 13618-13635, which has been published in final form at http://dx.doi.org/10.1002/chem.201402273. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for self-archiving.





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