Efficient Nonlinear Absorbing Platinum(II) Acetylide Chromophores in Solid PMMA Matrices

Platinum(II) acetylides were incorporated into poly(methyl methacrylate) (PMMA) glasses to obtain solid‐state nonlinear optical devices. We report on device fabrication, structural, chemical, and mechanical properties, as well as the optical limiting capabilities of the final solids. Two different guest‐host systems are presented: 1) Dye molecules functionalized to be readily dispersed in methyl methacrylate (MMA) and subsequent in situ polymerization of the MMA yielding solid PMMA host matrices. 2) Dye molecules functionalized to copolymerize with MMA forming covalent bonds between the guest and the PMMA host matrix. A range of doped organic solids were prepared, reaching concentrations up to 13 wt% of the guest molecule. Raman spectra of the doped solid devices indicate that the chemical structure of the nonlinear dyes remains intact upon the polymerization of the solid matrix. Luminescence spectra confirm that the basic photophysical properties observed for the same solute molecules in THF are maintained also in the solid state. Optical power limiting (OPL) characterization reveal clamping levels for the dyes nonbonded to the solid host being less than 4 µJ at pulse energies up to 110 µJ at 532 nm (f/5 arrangement and 5 ns pulses), which is comparable to the performance of similar dyes in THF solutions. In contrast, the highly crosslinked solid possesses a higher clamping level (8 µJ) at the same nominal concentration.