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

Lei Ji, Robert M. Edkins, Laura J Sewell, Andrew Beeby, Andrei S. Batsanov, Katharina Fucke, Martin Drafz, Judith A.K. Howard, Odile Moutounet, Fatima Ibersiene, Abdou Boucekkine, Eric Furet, Zhiqiang Liu, Jean-Francois Halet, Claudine Katan, Todd B. Marder

Research output: Contribution to journalArticlepeer-review

81 Citations (Scopus)

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.
Original languageEnglish
Pages (from-to)13618-13635
JournalChemistry - A European Journal
Volume20
Issue number42
Early online date28 Aug 2014
DOIs
Publication statusPublished - 13 Oct 2014

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