Theoretical and Experimental Study on Boron β‐Diketonate Complexes with Intense Two‐Photon‐Induced Fluorescence in Solution and in the Solid State. Issue 14 (18th April 2016)

• Record Type: Journal Article
• Authors: Lanoë, Pierre‐Henri; Mettra, Bastien; Liao, Yuan Yuan; Calin, Nathalie; D'Aléo, Anthony; Namikawa, Tomotaka; Kamada, Kenji; Fages, Fréderic; Monnereau, Cyrille; Andraud, Chantal
• Is Part Of: Chemphyschem. Volume 17:Issue 14(2016)
• Page Start: 2128
• Page End: 2136
• Publication Date: 2016-04-18
• Subjects: boron -- chromophores -- fluorescence -- solid-state emission -- theoretical calculations; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.201600178
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: Three boron diketonate chromophores with extended π‐conjugated backbone were prepared and their spectroscopic features were investigated through a combined theoretical/experimental study. It was shown that these complexes, which undergo very large electronic reorganization upon photoexcitation, combine large two‐photon absorption cross section with an emission energy and quantum efficiency in solution that is strongly dependent on solvent polarity. The strong positive influence of boron complexation on the magnitude of the two‐photon absorption was clearly established, and it was shown that the two‐photon absorption properties were dominated by the quadrupolar term. For one of the synthesized compounds, intense one‐ and two‐photon‐induced solid‐state emission (fluorescence quantum yield of 0.65 with maximum wavelength of 610 nm) was obtained as a result of antiparallel J‐aggregate crystal packing. Abstract : Getting excited ! The linear and nonlinear optical properties of three two‐photon‐absorbing, fluorescent boron diketonate complexes are unraveled through a combined spectroscopic and computational study. All three compounds display intense two‐photon absorption (200–1200 GM) in the near‐IR range ( λ =700–1100 nm), along with emission quantum yields that exceed 0.6 and that can reach unity in toluene.