Polymer Monoliths Containing Two-Photon Absorbing Phenylenevinylene Platinum(II) Acetylide Chromophores for Optical Power Limiting

Abstract

A series of platinum(II) acetylide complexes containing p-phenylenevinylene and moieties end-capped with triphenylamine groups have been incorporated into poly(methyl methacrylate) (PMMA) monoliths for optical power limiting applications. The one- and two-photon photophysical properties were investigated and compared to the photophysical properties in THF. The absolute two-photon absorption cross-section values for the monolith samples were measured and are comparable to the values obtained in solution. In the PMMA monoliths, the complexes retained the important two-photon absorption and reverse saturable absorption properties necessary for optical power limiting via dual mode mechanism, and their strong nonlinear absorption property was demonstrated by the open-aperture Z-scan method. Photostability studies of the p-phenylenevinylene platinum(II) acetylide complexes showed two photodegradation processes: a trans-to-cis isomerization and a singlet-oxygen sensitized self-oxidative cleavage. The photostability of the least photostable complex TPV0 was increased upon incorporation into a PMMA matrix.

Optical Properties of Hybrid Organic‐Inorganic Materials and their Applications

“…[294,[349][350][351][352][353][354][355][356][357][358] The use of PMMA monoliths hosting platinum derivatives was an efficient route towards OPL materials. [278,359] The measured linear transmissions were nearly 90% in the visible and NLO properties were maintained in the solid. The structural rigidity in the case of grafted dyes limited possibilities of relaxation compared to host-guest systems, leading to a loss of efficiency.…”

Crystal structure of 4,4′-((1Z,1′Z)-2,2′-(2,5-diethoxy-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine, C24H24N2O2

“…The oligo(phenylene vinylene) derivatives (OPVs) are important materials in the fields of nonlinear optics [5,6], solid state opto-electronics [7] and molecular devices [8].…”

How to assess good candidate molecules for self-activated optical power limiting

“…24,30 Pt-acetylides have been doped into PMMA (polymethyl methacrylate) matrices, producing OPL filters of good optical quality. 24,31,32 By a more recent sol-gel method, MTEOS (methyltriethoxysilane) glasses have been created with extremely high concentrations of Pt-acetylides of up to 400 mM. 30 The solubility of chromophores and the dispersion ability of nanoparticles are vital properties in the preparation of doped glasses.…”