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Organic and organometallic compounds for nonlinear absorption of light
Umeå University, Faculty of Science and Technology, Chemistry.
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 [en]
Organic chemistry, Nonlinear absorption, thiophene, platinum complexes, optical limiting, sonogashira coupling reactions, molecular orbital calculations
Keyword [sv]
Organisk kemi
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-965ISBN: 91-7264-243-2 (print)OAI: oai:DiVA.org:umu-965DiVA: diva2:145218
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
List of papers
1. A QSPR study on optical limiting of organic compounds
Open this publication in new window or tab >>A QSPR study on optical limiting of organic compounds
2004 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 387, no 4-6, 238-242 p.Article in journal (Refereed) Published
Abstract [en]

The optical limiting performance of 23 structurally different organic compounds has been measured at the wavelength of 532 nm. Molecular orbital ab initio calculations were performed to generate molecular electronic variables that were applied in a quantitative structure–property relationship (QSPR) study. A model that predicts the optical limiting response was constructed by using a partial least square (PLS) analysis. Six variables that play a major role for the optical limiting ability of organic materials were identified.

 

Place, publisher, year, edition, pages
Amsterdam: North-Holland Publishing Co, 2004
Identifiers
urn:nbn:se:umu:diva-5633 (URN)doi:10.1016/j.cplett.2004.02.023 (DOI)
Available from: 2007-01-04 Created: 2007-01-04 Last updated: 2017-12-14Bibliographically approved
2. Non-linear absorption of 2,5-dialkynyl thiophenes
Open this publication in new window or tab >>Non-linear absorption of 2,5-dialkynyl thiophenes
2005 (English)In: Journal of Physical Organic Chemistry, ISSN 0894-3230, E-ISSN 1099-1395, Vol. 18, no 5, 426-433 p.Article in journal (Refereed) Published
Abstract [en]

Three diarylalkynyl-substituted thiophenes were synthesized and the optical power limiting (OPL) effect at 532 nm was investigated for solutions of these compounds. The relationship between the OPL and parameters obtained from molecular-orbital-based calculations is discussed. Semi-empirical calculations indicate that the compounds can have a broad distribution of conformations due to inter-ring twisting, but that the second hyperpolarizability (gamma) can be significant despite a ring twist. The calculations imply that substitution by alkyl groups can lead to enhanced gamma values. The measurements and calculations show a greater increase of the OPL and gamma effects from compound 5 to 6 than from 6 to 7. For these compounds, which differ mainly by the length of the pi-electron system, the magnitude of non-linear absorption seems to be well correlated with several properties of the electronic ground state estimated by standard ab initio molecular orbital calculations, as well as with gamma values from the semi-empirical calculations.

Place, publisher, year, edition, pages
Chichester, Sussex, England: Wiley, 2005
Keyword
optical limiting, non-linear absorption, hyperpolarizability, thiophenes, thiophenyl, phenylacetylenes
Identifiers
urn:nbn:se:umu:diva-5634 (URN)doi:10.1002/poc.881 (DOI)
Available from: 2007-01-04 Created: 2007-01-04 Last updated: 2017-12-14Bibliographically approved
3. A theoretical and experimental study of non-linear absorption properties of substituted 2,5-di-(phenylethynyl) thiophenes and structurally related compounds
Open this publication in new window or tab >>A theoretical and experimental study of non-linear absorption properties of substituted 2,5-di-(phenylethynyl) thiophenes and structurally related compounds
Show others...
Manuscript (Other academic)
Identifiers
urn:nbn:se:umu:diva-5635 (URN)
Available from: 2007-01-04 Created: 2007-01-04 Last updated: 2010-01-13Bibliographically approved
4. 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

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