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Structural, photophysical, and nonlinear absorption properties of trans-di-arylalkynyl Platinum(II) Complexes with Phenyl and Thiophenyl Groups
Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics, Energy Technology and Thermal Process Chemistry.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics, Energy Technology and Thermal Process Chemistry.
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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.

Place, publisher, year, edition, pages
2007. Vol. 111, no 9, 1598-1609 p.
Identifiers
URN: urn:nbn:se:umu:diva-12651DOI: doi:10.1021/jp066569pPubMedID: 17290976OAI: oai:DiVA.org:umu-12651DiVA: diva2:152322
Available from: 2007-04-17 Created: 2007-04-17 Last updated: 2011-01-27Bibliographically approved
In thesis
1. Synthesis and optical characterization of optical power limiting platinum(II) acetylides
Open this publication in new window or tab >>Synthesis and optical characterization of optical power limiting platinum(II) acetylides
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
Platinum acetylides, nonlinear absorption, optical power limiting, Sonogashira coupling, solution gels, thiophene
National Category
Organic Chemistry
Identifiers
urn:nbn:se:umu:diva-1130 (URN)978-91-7264-290-4 (ISBN)
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
2. Organic and organometallic compounds for nonlinear absorption of light
Open this publication in new window or tab >>Organic and organometallic compounds for nonlinear absorption of light
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The demand for protection of eyes and various types of optical sensors from laser-beam pulses has resulted in the search for optical limiting devices that have the property of being transparent at low intensity of light (normal light), but non-transparent towards high intensity (laser) light. This type of protection may be obtained by using an organic material that displays nonlinear optical (NLO) properties. Examples of NLO effects that can be used for optical limiting are reverse saturable absorption (RSA), two-photon absorption (TPA) and nonlinear refraction.

The advantage of using compounds that show such NLO effects is that they can have very fast response and are self-activating, that is, there is no need for externally controlled switching to obtain optical limiting.

In this work, several dialkynyl substituted thiophenes and some thiophenyl-alkynyl-platinum(II)-complexes were synthesized and tested for nonlinear absorption of light. A palladium-copper mediated coupling (Sonogashira coupling) was utilized for all reactions between terminal alkynes and aryl halides.

Molecular orbital calculations were used in order to screen for suitable properties, such as the second hyperpolarizability, in compounds of interest.

A quantitative structure-activity relationship (QSPR) study using a PLS approach were performed in order to identify important molecular electronic variables for optical limiting of organic compounds.

Place, publisher, year, edition, pages
Umeå: Kemi, 2007. 84 p.
Keyword
Organic chemistry, Nonlinear absorption, thiophene, platinum complexes, optical limiting, sonogashira coupling reactions, molecular orbital calculations, Organisk kemi
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:umu:diva-965 (URN)91-7264-243-2 (ISBN)
Public defence
2007-01-26, KB3B1, KBC, Umeå universitet, Umeå, 10:00 (English)
Opponent
Supervisors
Available from: 2007-01-04 Created: 2007-01-04 Last updated: 2009-09-07Bibliographically approved

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Boström, DanCarlsson, MarcusEliasson, Bertil

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