SEARCH

SEARCH BY CITATION

Keywords:

  • Dyes;
  • Fluorescence;
  • Lasing

Abstract

In the search for more efficient and photostable solid-state dye lasers, newly synthesized analogs of the borondipyrromethene (BODIPY) dye PM567, bearing the polymerizable methacryloyloxypropyl group at position 2 (PMoMA) or at positions 2 and 6 (PDiMA), have been studied in the form of solid copolymers with methyl methacrylate (MMA). The parent dye PM567, as well as the model analogs bearing the acetoxypropyl group in the same positions, PMoAc and PDiAc, respectively, have been also studied both in liquid solvents and in solid poly(MMA) (PMMA) solution. Although in liquid solution PMoAc and PDiAc have the same photophysical properties as PM567, PDiAc exhibited a photostability up to 10 times higher than that of PM567 in ethanol under 310 nm-irradiation. The possible stabilization factors of PDiAc have been analyzed and discussed on the basis of the redox potentials, the ability for singlet molecular oxygen [O2(1Δg)] generation, the reactivity with O2(1Δg), and quantum mechanical calculations. Both PMoAc and PDiAc, pumped transversally at 532 nm, lased in liquid solution with a high (up to 58 %), near solvent-independent efficiency. This enhanced photostabilization has been also observed in solid polymeric and copolymeric media. While the solid solution of the model dye PDiAc in PMMA showed a lasing efficiency of 33 %, with a decrease in the laser output of ca. 50 % after 60 000 pump pulses (10 Hz repetition rate) in the same position of the sample, the solid copolymer with the double bonded chromophore, COP(PDiMA-MMA), showed lasing efficiencies of up to 37 %, and no sign of degradation in the laser output after 100 000 similar pump pulses. Even under the more demanding repetition rate of 30 Hz, the laser emission from this material remained at 67 % of its initial laser output after 400 000 pump pulses, which is the highest laser photostability achieved to date for solid-state lasers based on organic polymeric materials doped with laser dyes. This result indicates that the double covalent linkage of the BODIPY chromophore to a PMMA polymeric matrix is even more efficient than the simple linkage, for its photostabilization under laser operation.