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 François Halet, Claudine Katan, Todd B. Marder

Research output: Contribution to journalArticle

42 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.

LanguageEnglish
Pages13618-13635
Number of pages18
JournalChemistry - A European Journal
Volume20
Issue number42
DOIs
Publication statusPublished - 1 Oct 2014

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Chromophores
Thiophenes
Thiophene
Photons
Fluorescence
Discrete Fourier transforms
Absorption spectra
Quantum yield
Photoluminescence
Coloring Agents
Dyes
Crystal structure

Keywords

  • boron
  • density functional calculations
  • luminescence
  • nonlinear optics
  • photophysics

Cite this

Ji, Lei ; Edkins, Robert M. ; Sewell, Laura J. ; Beeby, Andrew ; Batsanov, Andrei S. ; Fucke, Katharina ; Drafz, Martin ; Howard, Judith A.K. ; Moutounet, Odile ; Ibersiene, Fatima ; Boucekkine, Abdou ; Furet, Eric ; Liu, Zhiqiang ; Halet, Jean François ; Katan, Claudine ; Marder, Todd 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. In: Chemistry - A European Journal . 2014 ; Vol. 20, No. 42. pp. 13618-13635.
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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.",
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author = "Lei Ji and Edkins, {Robert M.} and Sewell, {Laura J.} and Andrew Beeby and Batsanov, {Andrei S.} and Katharina Fucke and Martin Drafz and Howard, {Judith A.K.} and Odile Moutounet and Fatima Ibersiene and Abdou Boucekkine and Eric Furet and Zhiqiang Liu and Halet, {Jean Fran{\cc}ois} and Claudine Katan and Marder, {Todd B.}",
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Ji, L, Edkins, RM, Sewell, LJ, Beeby, A, Batsanov, AS, Fucke, K, Drafz, M, Howard, JAK, Moutounet, O, Ibersiene, F, Boucekkine, A, Furet, E, Liu, Z, Halet, JF, Katan, C & Marder, TB 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 , vol. 20, no. 42, pp. 13618-13635. https://doi.org/10.1002/chem.201402273

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

In: Chemistry - A European Journal , Vol. 20, No. 42, 01.10.2014, p. 13618-13635.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Experimental and theoretical studies of quadrupolar oligothiophene-cored chromophores containing dimesitylboryl moieties as π-accepting end-groups

T2 - Chemistry - A European Journal

AU - Ji, Lei

AU - Edkins, Robert M.

AU - Sewell, Laura J.

AU - Beeby, Andrew

AU - Batsanov, Andrei S.

AU - Fucke, Katharina

AU - Drafz, Martin

AU - Howard, Judith A.K.

AU - Moutounet, Odile

AU - Ibersiene, Fatima

AU - Boucekkine, Abdou

AU - Furet, Eric

AU - Liu, Zhiqiang

AU - Halet, Jean François

AU - Katan, Claudine

AU - Marder, Todd B.

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N2 - 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.

AB - 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.

KW - boron

KW - density functional calculations

KW - luminescence

KW - nonlinear optics

KW - photophysics

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