title: Electrochemical, linear optical, and nonlinear optical properties and interpretation by density functional theory calculations of (4-N,N-dimethylaminostyryl)-pyridinium pendant group associated with polypyridinic ligands and respective multifunctional metal complexes (Ru(II) or Zn(II)).
abstract: The synthesis, linear optical and nonlinear optical properties, as well as the electrochemical behavior of a series of pro-ligands containing the 4-(4-N,N-dimethylaminostyryl)-1-methyl pyridinium (DASP(+)) group as a push-pull moiety covalently linked to terpyridine or bipyridine as chelating ligands are reported in this full paper. The corresponding multifunctional Ru(II) and Zn(II) complexes were prepared and investigated. The structural, electronic, and optical properties of the pro-ligands and the ruthenium complexes were investigated using density functional theory (DFT) and time-dependent (TD) DFT calculations. A fairly good agreement was observed between the experimental and the calculated electronic spectra of the pro-ligands and their corresponding ruthenium complexes. A quenching of luminescence was evidenced in all ruthenium complexes compared with the free pro-ligands but even the terpyridine-functionalized metal complexes exhibited detectable luminescence at room temperature. Second order nonlinear optical (NLO) measurements were performed by Harmonic Light Scattering and the contribution of the DASP(+) moieties (and their relative ordering) and the metal-polypyridyl core need to be considered to explain the nonlinear optical properties of the metal complexes.
authors: Institut Lavoisier de Versailles, UMR-CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 78035 Versailles, France.
authors: Frédéric
authors: F
authors: Dumur
authors: Cédric R
authors: CR
authors: Mayer
authors: Khuyen
authors: K
authors: Hoang-Thi
authors: Isabelle
authors: I
authors: Ledoux-Rak
authors: Fabien
authors: F
authors: Miomandre
authors: Gilles
authors: G
authors: Clavier
authors: Eddy
authors: E
authors: Dumas
authors: Rachel
authors: R
authors: Méallet-Renault
authors: Michel
authors: M
authors: Frigoli
authors: Joseph
authors: J
authors: Zyss
authors: Francis
authors: F
authors: Sécheresse
mesh_terms: D003198:Computer Simulation; D004563:Electrochemistry; D008024:Ligands; D008956:Models, Chemical; D015394:Molecular Structure; D055095:Optics and Photonics; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D011726:Pyridinium Compounds / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: C032315:4-(4-dimethylaminostyryl)-1-methylpyridinium; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D011726:Pyridinium Compounds; D012428:Ruthenium; D015032:Zinc