Direct Synthesis of 2, 5‐Bis(dodecanoxy)phenyleneethynylene‐Butadiynes by Sonogashira Coupling Reaction. Issue 24 (8th July 2013)

• Record Type: Journal Article
• Authors: Arias, Eduardo; Moggio, Ivana; Torres, Román; Ziolo, Ronald F.; Maldonado, José‐Luis; Green, Kirk; Cooper, Thomas M.; Wicks, Geoffrey; Rebane, Aleksander; Drobizhev, Mikhail; Makarov, Nikolay S.; Ottonelli, Massimo; Dellepiane, Giovanna
• Is Part Of: European journal of organic chemistry. Issue 24(2013)
• Page Start: 5341
• Page End: 5352
• Publication Date: 2013-07-08
• Subjects: Alkynes -- Conjugation -- Chain structures -- Nonlinear optics -- UV/Vis spectroscopy; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201300230
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: The synthesis of a 2, 5‐bis(dodecanoxy)phenyleneethynylene‐butadiyne series with 2, 4, 6 and 8 phenyl rings is reported. Sonogashira coupling reaction, rather than the Glaser/Eglinton/Hay reactions classically used for butadiyne formation was applied. The molecular structures of all compounds were confirmed by 1 H, DEPT‐135, APT 13 C, MALDI‐TOF, FTIR and FT‐Raman analyses. The linear and nonlinear optical properties were studied in solution by UV/Vis, static and time‐resolved fluorescence, and by two‐photon absorption (2PA) spectroscopy. With the exception of the dimer, for which intersystem crossing is very favoured due to the low energy gap between the singlet and triplet states as theoretically predicted, the other oligomers present high fluorescence quantum yields (0.77–0.82) and large cross‐sections (up to 5000 GM for the octamer) that could be applied in multiphoton microscopy or nonlinear optics. Abstract : An alternative strategy that can be used to obtain phenyleneethynylene‐butadiynes through Sonogashira reaction is reported. A combined spectroscopic and theoretical study reveals that the dimer behaves like a diacetylene, whereas the longer oligomers present large quantum yield due to larger energy gaps between the singlet and triplet excited states.