The effect of dendritic substituents on a nonlinear optical chromophore for optical power limiting (OPL) has been investigated. Synthesis and characterization of bis((4-(phenylethynyl)phenyl)ethynyl)bis-(tributylphosphine)platinum(II) with dendritic end groups are described. Polyester dendrimers up to the fourth generation were grown divergently using the anhydride of 2,2-bis(methylol)propionic acid (bis-MPA). The introduction of the dendritic moieties onto the NLO chromophore enables further processing of the materials using polymeric and related techniques. OPL measurements performed at 532, 580, and 630 nm show that the OPL properties improve with increasing size of the dendritic substituent. It is also shown that the addition of the dendrons increase the OPL as compared to the nondecorated bis((4-(phenylethynyl)phenyl)ethynyl)bis-(tributylphosphine)platinum(II). By use of femtosecond z-scan measurements carried out at different pulse-repetition frequencies, it is shown that the two-photon absorption cross section is ∼10 GM. Using pulse repetition frequencies (100 kHz-4.75 MHz) so that the time between the pulses is comparable with the triplet excited lifetime, the z-scans become dominated by excited-state absorption of excited triplet states.

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.