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Synthesis and development of compounds for nonlinear absorption of light
Umeå University, Faculty of Science and Technology, Department of Chemistry. (Bertil Eliasson)
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

High-intensity light — for instance that from a laser — can be destructive, not only to the human eye, but also to equipment such as imaging sensors and optical communication devices. Therefore, effective protection against such light is desirable. A protection device should ideally have high transmission to non-damaging light, and should also be fast-acting in order to effectively stop high-intensity light.

In working towards a protection device, there is a need to conduct fundamental research in order to understand the processes involved. One of the photophysical processes of special interest in the field of optical power limiting (OPL) is reverse saturable absorption, where a compound in an excited state absorbs light more strongly than it does in its ground state.

In this work, several novel organoplatinum compounds for OPL, rationally designed to have a strong reverse saturable absorption, have been synthesized. The compounds have been analyzed using linear and nonlinear absorption spectroscopy, luminescence spectroscopy, and quantum chemistry calculations to gain further knowledge regarding their photophysical properties.

In addition to this fundamental research, the absorption capabilities of some of these compounds indicate that they can be used for OPL applications. Consequently, compounds from these studies have been incorporated into a sol–gel glass that could be used in optical systems.

Place, publisher, year, edition, pages
Umeå: Umeå universitet , 2012. , 50 p.
Keyword [en]
Platinum acetylide, nonlinear absorption, optical power limiting, oxazole, quantum chemistry calculation, quantum chemical calculation, triplet absorption
National Category
Organic Chemistry
Research subject
Organic Chemistry; Physical Chemistry; Quantum Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-60190ISBN: 978-91-7459-503-1 (print)OAI: oai:DiVA.org:umu-60190DiVA: diva2:559458
Public defence
2012-11-02, KBC-huset, KB3A9, Umeå universitet, Umeå, 10:00 (English)
Opponent
Supervisors
Note

Finansiellt stöd från Kempestiftelsen.

Available from: 2012-10-12 Created: 2012-10-04 Last updated: 2012-10-09Bibliographically approved
List of papers
1. Luminescence, singlet oxygen production, and optical power limiting of some diacetylide platinum(II) diphosphine complexes
Open this publication in new window or tab >>Luminescence, singlet oxygen production, and optical power limiting of some diacetylide platinum(II) diphosphine complexes
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2010 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 114, no 10, 3431-3442 p.Article in journal (Refereed) Published
Abstract [en]

A series of four new trans-diphosphine Pt(II) diacetylide complexes, with a thiophene and two benzenoid rings in each acetylide ligand, have been synthesized and characterized with respect to optical absorption, spectrally and time-resolved luminescence, and optically nonlinear properties such as two-photon absorption cross section and optical power limiting. Density functional theory (DFT) calculations of a few ground state conformations of three Pt(II) diacetylide structures showed similar total energy for each geometry-optimized rotamer but some differences in the vertical excitation energies and in the ligand-to-metal charge-transfer character. The wavelengths of the calculated excitations were found to be red-shifted compared with peaks in the optical absorption spectra, but the general trends and shifts of wavelengths between the different structures are well reproduced. Static emission spectra for degassed samples in THF solution of the larger compounds showed small Stokes shifts and low fluorescence quantum yields, indicating fast intersystem crossing to the triplet manifold. More pronounced differences between the compounds were displayed in the phosphorescence data, in terms of spectral emission wavelengths and decay times. For instance, the phosphorescence decay of the compound with the thiophene ring close to the Pt center was found to be significantly faster than for the other compounds. A possible relationship between triplet lifetime and conformation of the compounds is discussed. It was also demonstrated that the quenching of the excited triplet states in air-saturated samples involves energy transfer to the oxygen triplet state, and subsequent generation of singlet oxygen showing the typical emission at approximately 1275 nm. The amount of produced singlet oxygen followed the phosphorescence yields of the solute molecules. Two-photon absorption cross sections (sigma(2)) were measured and showed values on the order of 10 GM at 780 nm for all compounds. Optical power limiting measurements of the new complexes in THF using 5 ns pulses, showed only slightly better performance at the wavelength of 532 nm compared to that of similar platinum compounds with only two aryl rings in each ligand. At 600 nm the complexes with three aryl rings were significantly better optical limiters than the smaller compounds with two aryl rings in the ligands.

Place, publisher, year, edition, pages
ACS Publications, 2010
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-34222 (URN)10.1021/jp9091514 (DOI)000275327600008 ()20148542 (PubMedID)
Available from: 2010-05-21 Created: 2010-05-21 Last updated: 2012-10-09Bibliographically approved
2. Silica hybrid sol-gel materials with unusually high concentration of Pt-organic molecular guests: Studies of luminescence and nonlinear absorption of light
Open this publication in new window or tab >>Silica hybrid sol-gel materials with unusually high concentration of Pt-organic molecular guests: Studies of luminescence and nonlinear absorption of light
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2012 (English)In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 4, no 5, 2369-2377 p.Article in journal (Refereed) Published
Abstract [en]

The development of new photonic materials is a key step towards improvement of existing optical devices and for the preparation of a new generation of systems. Therefore synthesis of photonic hybrid materials with a thorough understanding and control of the microstructure-to-properties relationships is crucial. In this perspective, a new preparation method based on fast gelation reactions using simple dispersion of dyes without strong covalent bonding between dye and matrix has been developed. This new sol-gel method is demonstrated through synthesis of monolithic siloxane-based hybrid materials highly doped by various platinum(II) acetylide derivatives. Concentrations of the chromophores as high as 400 mM were obtained and resulted in unprecedented optical power limiting (OPL) performance at 532 nm of the surface-polished solids. Static and time-resolved photoluminescence of the prepared hybrid materials were consistent with both OPL data and previous studies of similar Pt(II) compounds in solution. The impacts of the microstructure and the chemical composition of the matrix on the spectroscopic properties, are discussed.

Place, publisher, year, edition, pages
Washington: American Chemical Society (ACS), 2012
Keyword
sol−gel, hybrid materials, xerogel, monolith, nonlinear absorption, optical power limiting, platinum
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-54413 (URN)10.1021/am2015537 (DOI)22276683 (PubMedID)
Available from: 2012-04-26 Created: 2012-04-26 Last updated: 2017-12-07Bibliographically approved

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