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Synthesis and optical characterization of optical power limiting platinum(II) acetylides
Umeå University, Faculty of Science and Technology, Chemistry.
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Interactions between light and a molecule can result in reversible or irreversible changes in properties of both the light and the molecule. Of the many known interactions, nonlinear absorption is a process in which an intense light signal, for instance from a laser, can be moderated. This can be manifested either in a marked lowering of the light’s intensity or in reductions in fluctuations of its intensity. Such an effect is often termed ‘optical power limiting’ (OPL).

High power lasers can be very dangerous since their high intensity can damage or destroy eyes and optical sensors. However, there are currently no adequate protective measures against lasers that cover the entire visible region and there is an increasing demand for new or improved OPL materials. Some of the most promising optical power limiting materials are substances that combine nonlinear optical properties with high transparency in normal light, but after activation by a laser beam, their light transmittance falls extremely rapidly via so-called self-activating mechanisms. The platinum(II) acetylides comprise one class of compounds with such properties.

In this study, various OPL Pt(II) acetylides were synthesized and their nonlinear optical properties were characterized. The emphasis of the work was on preparation of the compounds, but in order to design organoplatinum chromophores for OPL, attempts were also made to obtain insight into the mechanisms of nonlinear absorption.

The work was divided into two main parts. In the first the goal was to find compounds that are good optical limiters in solution. The possibility of isolating the chromophore site by dendron shielding and the effects of incorporating a thiophene ring into the organic molecular system were also explored. In addition, a new route for synthesizing these compounds was developed. The second part was focused on incorporating the most interesting compounds into solid materials. The preparation and characterization of Pt(II) acetylides with molecular groups for covalent attachment to a silica matrix via the solution gel approach is described.

Place, publisher, year, edition, pages
Umeå: Kemi , 2007. , 58 p.
Keyword [en]
Platinum acetylides, nonlinear absorption, optical power limiting, Sonogashira coupling, solution gels, thiophene
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-1130ISBN: 978-91-7264-290-4 (print)OAI: oai:DiVA.org:umu-1130DiVA: diva2:140316
Public defence
2007-06-01, KB3B1, KBC, Umeå, 10:00 (English)
Opponent
Supervisors
Available from: 2007-05-10 Created: 2007-05-10 Last updated: 2009-09-07Bibliographically approved
List of papers
1. Structural, photophysical, and nonlinear absorption properties of trans-di-arylalkynyl Platinum(II) Complexes with Phenyl and Thiophenyl Groups
Open this publication in new window or tab >>Structural, photophysical, and nonlinear absorption properties of trans-di-arylalkynyl Platinum(II) Complexes with Phenyl and Thiophenyl Groups
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2007 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 111, no 9, 1598-1609 p.Article in journal (Refereed) Published
Abstract [en]

Optical power limiting and luminescence properties of two Pt(II) complexes with thiophenyl and phenyl groups in the ligands, trans-Pt(P(n-Bu)3)2(C[triple bond]C-Ar)2, where Ar = -C4H2S-C[triple bond]C-p-C6H4-n-C5H11 (1) and -p-C6H4-C[triple bond]C-C4H3S (2), have been investigated. The fluorescence lifetimes were found to be on the sub-nanosecond time scale, and the quantum yields were low, in accord with fast intersystem crossing from the excited singlet to triplet manifold. The phosphorescence lifetimes of 1 and 2 were shorter than that of a Pt(II) complex having two phenyl groups in the ligands. In order to elucidate the C-Pt bonding nature in the ground state, the 13C NMR chemical shift of the carbon directly bonded to Pt, the coupling constants 1JPtC, 2JPtC, and 1JPtP, and IR νC[triple bond]C wavenumbers were obtained for 1, 2, and three other trans-diarylalkynyl Pt(II) complexes. X-ray diffraction data of 1 and 2 and density functional theory calculated geometries of models of 1, 2, and trans-Pt(P(n-Bu)3)2(C[triple bond]C-p-C6H4-C[triple bond]C-C6H5)2 (3) show that 1 preferably exists in a different conformation from that of 2 and 3. The variations in photophysical, NMR, and IR data can be rationalized by differences in geometry and pi-backbonding from Pt to the alkynyl ligand.

Identifiers
urn:nbn:se:umu:diva-12651 (URN)doi:10.1021/jp066569p (DOI)17290976 (PubMedID)
Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved
2. Synthesis of diacetylide platinum(II) diphosphine complexes and nonlinear absorption of light
Open this publication in new window or tab >>Synthesis of diacetylide platinum(II) diphosphine complexes and nonlinear absorption of light
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Manuscript (Other academic)
Identifiers
urn:nbn:se:umu:diva-2355 (URN)
Available from: 2007-05-10 Created: 2007-05-10 Last updated: 2010-01-13Bibliographically approved
3. Dendron Decorated Platinum(II) Acetylides for Optical Power Limiting
Open this publication in new window or tab >>Dendron Decorated Platinum(II) Acetylides for Optical Power Limiting
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2006 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 39, no 6, 2238-2246 p.Article in journal (Refereed) Published
Abstract [en]

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.

Identifiers
urn:nbn:se:umu:diva-12745 (URN)doi:10.1021/ma0523670 (DOI)
Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2017-12-14Bibliographically approved
4. One-pot synthesis of trans mono- or diarylalkynyl substituted platinum(II) compounds with tertiary phosphine or phosphite ligands
Open this publication in new window or tab >>One-pot synthesis of trans mono- or diarylalkynyl substituted platinum(II) compounds with tertiary phosphine or phosphite ligands
2006 (English)In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 25, no 22, 5500-5502 p.Article in journal (Refereed) Published
Abstract [en]

An efficient one-pot synthesis has been developed for preparation of trans-mono- or diarylalkynyl bisphosphine or bisphosphite Pt(II) compounds. In the procedure, the alkyne and the tertiary phosphorus ligands are mixed with PtCl2 in tetrahydrofuran and triethylamine solution. CuI is added for synthesis of disubstituted complexes, but the catalyst is not used for preparation of monosubstituted complexes. Microwave irradiation is preferably employed to give the trans-mono- or diarylalkynyl Pt(II) compound in short time and high yield.

Identifiers
urn:nbn:se:umu:diva-2357 (URN)doi:10.1021/om060616i (DOI)
Available from: 2007-05-10 Created: 2007-05-10 Last updated: 2017-12-14Bibliographically approved
5. Synthesis of di(arylethynyl)bis(tributylphosphine) platinum(II) complexes and preparation of organic-inorganic hybrid silica glass for nonlinear absorption of light
Open this publication in new window or tab >>Synthesis of di(arylethynyl)bis(tributylphosphine) platinum(II) complexes and preparation of organic-inorganic hybrid silica glass for nonlinear absorption of light
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(English)Manuscript (preprint) (Other (popular science, discussion, etc.))
Identifiers
urn:nbn:se:umu:diva-2358 (URN)
Available from: 2007-05-10 Created: 2007-05-10 Last updated: 2010-01-14Bibliographically approved

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