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Efficient Nonlinear Absorbing Platinum(II) Acetylide Chromophores in Solid PMMA Matrices
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-8348-2273
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2008 (English)In: Advanced Functional Materials, ISSN 1616-301X, E-ISSN 1616-3028, Vol. 18, no 13, 1939-1948 p.Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2008. Vol. 18, no 13, 1939-1948 p.
Keyword [en]
Acrylic monomers, Chemical properties, Chemical reactions, Concentration (process), Covalent bonds, Crosslinking, Electron beam lithography, Esters, Light emission, Luminescence, Matrix algebra, Mechanical properties, Military seaplanes, Molecules, Monomers, Optical design, Optical instruments, Photoresists, Platinum, Polymer blends, Polymerization, Polymers, Seaplanes, Sulfur compounds
National Category
Chemical Engineering
URN: urn:nbn:se:kth:diva-9156DOI: 10.1002/adfm.200800265ISI: 000257808300010ScopusID: 2-s2.0-47949119549OAI: diva2:25341
QC 20100910Available from: 2008-09-25 Created: 2008-09-25 Last updated: 2010-09-20Bibliographically approved
In thesis
1. Nonlinear Absorbing platinum(II) Acetylides for Optical Power Limiting Applications
Open this publication in new window or tab >>Nonlinear Absorbing platinum(II) Acetylides for Optical Power Limiting Applications
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

During the past few decades, laser technology has had a strong impact on our society, providing important contributions to materials processing, data storage, communications, medicine, and defense applications. However, the progress in laser technology has also brought about the development of harmful portable high‐power lasers and tactical laser weapons. As a result, the hazard of being blinded by lasers (accidentally or from hostile use) has increased significantly. Hence, the need for protection against lasers has emerged. In order to protect optical sensors against harmful laser radiation, materials that absorb high intensity light, such as nonlinear absorbing chromophores, are employed. The concept of controlling the intensity of an optical light beam is usually referred to as optical power limiting and can be used efficiently in sensor protection devices.In this thesis, various nonlinear absorbing platinum(II) acetylides have been synthesized and characterized regarding their photophysical and optical limiting properties. Dendronized platinum(II) acetylides were prepared in order to evaluate the site isolation effect offered by the dendritic surrounding. The photophysical measurements reveal that the dendritic encapsulation enhances the phosphorescence, increases the luminescence lifetimes, and improves the optical limiting performance due to reduced quenching of the excited states.Triazole‐containing chromophores were synthesized using click chemistry to achieve functionalized platinum(II) acetylides. It was found that the position of the triazole unit affects the photophysical properties of these chromophores. The most promising results were obtained for the chromophore with the triazole located at the end of the conjugation where it may act as an electron donor, thus contributing to improved two‐photon absorption.A branched platinum(II) acetylide was also prepared in order to investigate the effect of multiple conjugated arms as well as multiple heavy atoms within the same molecule on the optical limiting performance. The star shaped chromophore reached the lowest clamping level of all compounds included in this thesis and constitutes a highly suitable chromophore for optical power limiting applications.The nonlinear absorbing chromophores were also incorporated into novel solid state materials based on PMMA. The actual device fabrication of doped organic glasses as optical limiters for sensor protection is presented, and their optical limiting performance is reported. The obtained organic glasses can reduce the transmission of high intensity light by 97 %.

Place, publisher, year, edition, pages
Stockholm: KTH, 2008. 73 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2008:59
optical power limiting
National Category
Polymer Chemistry
urn:nbn:se:kth:diva-9169 (URN)978-91-7415-102-2 (ISBN)
Public defence
2008-10-03, F3, Lindstedtsvägen 26, Stockholm, 10:15 (English)
QC 20100920Available from: 2008-09-30 Created: 2008-09-29 Last updated: 2010-09-20Bibliographically approved

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