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)).
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.
Dumur
Frédéric
F
Institut Lavoisier de Versailles, UMR-CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 78035 Versailles, France.
Mayer
Cédric R
CR
Hoang-Thi
Khuyen
K
Ledoux-Rak
Isabelle
I
Miomandre
Fabien
F
Clavier
Gilles
G
Dumas
Eddy
E
Méallet-Renault
Rachel
R
Frigoli
Michel
M
Zyss
Joseph
J
Sécheresse
Francis
F
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*
C032315:4-(4-dimethylaminostyryl)-1-methylpyridinium; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D011726:Pyridinium Compounds; D012428:Ruthenium; D015032:Zinc