title: Incorporation of a platinum center in the pi-conjugated core of push-pull chromophores for nonlinear optics (NLO).
abstract: In this article, we describe the synthesis, redox characteristics, and linear and nonlinear optical (NLO) properties of seven new unsymmetrical push-pull diacetylide platinum-based complexes. These D-π-Pt-π-A complexes incorporate pyranylidene ligands as pro-aromatic donor groups (D), diazine rings as electron-withdrawing groups (A), and various aromatic fragments (styryl or thienylvinyl) as π-linkers separating the platinum diacetylide unit from the donor and the acceptor groups. This is one of the first examples of push-pull chromophores incorporating a platinum center in the π-conjugated core. The NLO properties of these complexes were compared with those of their purely organic analogues. All compounds (organic and organometallic) exhibited positive μβ values, which dramatically increased upon methylation of the pyrimidine fragment. However, this increase was even more significant in the complexes due to the presence of platinum in the π-conjugated core. The effects of the linker on the redox and spectroscopic properties of the complexes are also discussed. In addition, DFT calculations were performed in order to gain further insight into the intramolecular charge transfer (ICT) occurring through the platinum center.
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, IUT de Lannion, rue Edouard Branly, BP 30219, F-22302 Lannion Cedex, France. sebastien.gauthier@univ-rennes1.fr sylvain.achelle@univ-rennes1.fr.
authors.forename: Raphaël J
authors.initials: RJ
authors.lastname: Durand
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, IUT de Lannion, rue Edouard Branly, BP 30219, F-22302 Lannion Cedex, France. sebastien.gauthier@univ-rennes1.fr sylvain.achelle@univ-rennes1.fr.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Gauthier
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, IUT de Lannion, rue Edouard Branly, BP 30219, F-22302 Lannion Cedex, France. sebastien.gauthier@univ-rennes1.fr sylvain.achelle@univ-rennes1.fr.
authors.forename: Sylvain
authors.identifier: http://orcid.org/0000-0002-9226-7735
authors.initials: S
authors.lastname: Achelle
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, Campus de Beaulieu, 263 av. Général Leclerc, 35042 Rennes, France.
authors.forename: Samia
authors.initials: S
authors.lastname: Kahlal
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, Campus de Beaulieu, 263 av. Général Leclerc, 35042 Rennes, France.
authors.forename: Jean-Yves
authors.initials: JY
authors.lastname: Saillard
authors.affiliation: Département d'Optique ultra-rapide et Nanophotonique, IPCMS-CNRS, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France.
authors.forename: Alberto
authors.initials: A
authors.lastname: Barsella
authors.affiliation: Laboratoire de Chimie, Électrochimie Moléculaires et Chimie Analytique, UMR CNRS 6521, Université de Bretagne Occidentale, UFR Sciences et Techniques, 6 avenue Victor Le Gorgeu - CS 93837, F-29238 Brest Cedex 3, France.
authors.forename: Laurianne
authors.initials: L
authors.lastname: Wojcik
authors.affiliation: Laboratoire de Chimie, Électrochimie Moléculaires et Chimie Analytique, UMR CNRS 6521, Université de Bretagne Occidentale, UFR Sciences et Techniques, 6 avenue Victor Le Gorgeu - CS 93837, F-29238 Brest Cedex 3, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Le Poul
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, IUT de Lannion, rue Edouard Branly, BP 30219, F-22302 Lannion Cedex, France. sebastien.gauthier@univ-rennes1.fr sylvain.achelle@univ-rennes1.fr.
authors.forename: Françoise
authors.initials: F
authors.lastname: Robin-Le Guen