conférences plénières

CPCQ2015, 31 mars-02 avril 2015
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CONFÉRENCES PLÉNIÈRES

CPCQ2015, 31 mars-02 avril 2015
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CPCQ2015, 31 mars-02 avril 2015
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Conférence Plénière 01
DFT STUDIES OF SPECTROSCOPIC, LUMINESCENCE AND NLO PROPERTIES OF
ORGANOMETALLIC COMPLEXES
Abdou Boucekkine
Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042
Rennes cedex (France); [e-mail]
Abstract: Luminescence and non linear optical (NLO) properties of organometallic complexes are
current domains of active research of many laboratories. The technological applications are
numerous in the fields of lasers, LED, etc. Standard Density Functional Theory (DFT) and Time
Dependent DFT (TD-DFT) calculations usually give a correct description of molecular ground state
properties like geometries, vibration frequencies, and of UV-visible spectra, and lead, at least, to a
correct qualitative estimate of NLO properties. In all cases, DFT computations could help to the
design of new molecules exhibiting improved properties. In this paper, several joint experimental and
theoretical studies will be presented, among them, second-order NLO switches based on
photochromic cyclometalated Pt(II) complexes, oligomerisation effect on excitation spectra of gold(I)
complexes, gold-gold bond formation under irradiation.
Keywords: DFT, TD-DFT, optical properties, NLO.
1- The triggering of the quadratic NLO response (strong enhancement of the NLO response upon
irradiation) of cyclometalated platinum (II) complexes based on a dithienylethene (DTE)
photochromic species (Figure 1) [1].
Figure 1: Second-Order NLO Switches Based on Photochromic Cyclometalated Pt(II) Complexes.

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2- The First HexaDithienylethene Tris (Bipyridine)Metal Complexes as Quadratic NLO
Photoswitches: Combined Experimental and DFT Studies (Figure 2) [2].
Figure 2: The first octupolar iron-based chromophore featuring six photochromic DTE units
3- Structure and Spectroscopic Properties of Gold (I) Diselenophosph(in)ate Complexes. A Joint
Experimental and Theoretical Study (Figure 3) [3].
It is shown using TD-DFT computations that their observed UV-visible excitation spectra in
solution are due to high oligomers and not to monomers or low size oligomers.
Figure 3: Computed optical absorption wavelengths vs. n in the [Au]2n oligomers (upper curve for the
highest excitation wavelength)

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4- Chemical Au-Au bonding induced by UV irradiation of dinuclear Gold (I) complexes. A
computational study with experimental evidence. (Figure 4) [4].
Figure 4 : Gold-Gold bond formation under UV irradiation.
5- Metal induced distortion of ligands upon complexation (Figure 5) [5]
Figure 5 : Theoretical evidence of metal-induced structural distortions in a series of bipyrimidine-
based ligands.
References
[1] J. Boixel, V. Guerchais, H. Le Bozec, D. Jacquemin, A. Amar, A. Boucekkine, A. Colombo, C.
Dragonetti, D. Marinotto, D. Roberto, S. Righetto, R. De Angelis, J. Am. Chem. Soc. 136 (2014)
5367−5375
[2] L. Ordronneau, V. Aubert, V. Guerchais, A. Boucekkine, H. Le Bozec, A. Singh, I. Ledoux, D.
Jacquemin, Chem. Eur. J. 19 (2013) 5845 –5849
[3] C. Latouche, Y-C. Lee, J-H. Liao, E. Furet, J-Y. Saillard, C. W. Liu, A. Boucekkine, Inorg. Chem. 51