Synthesis, Structures, And Optical Properties Of Ruthenium(Ii) Complexes Of The Tris(1-Pyrazolyl)Methane Ligand

Four new complex salts [(RuCl)-Cl-II(Tpm)(L-A)(2)][PF6](n) [TPm = tris(1-pyrazolyl)methane; n = 1, L-A = pyridine (py) 1 or ethyl isonicotinate (EIN) 2; n = 3, L-A = N-methyl-4,4'-bipyridinium (MeQ(+)) 3 or N-phenyl-4,4'-bipyridinium (PhQ(+)) 4] have been prepared and characterized. Electronic absorption spectra show intense d -> pi* metal-to-ligand charge-transfer (MLCT) absorption bands, while cyclic voltammetry reveals a reversible Ru-III/II wave, accompanied by quasireversible or irreversible L-A-based reductions for all except 1. Single crystal X-ray structures have been obtained for 1 center dot Me2CO, 2, and 3 center dot Me2CO. For 2-4, molecular first hyperpolarizabilities beta have been measured in acetonitrile solutions via the hyper-Rayleigh scattering (HRS) technique at 800 nm. Stark (electroabsorption) spectroscopic studies on the MLCT bands in frozen butyronitrile allow the indirect estimation of static first hyperpolarizabilities beta(0). The various physical data obtained for 3 and 4 are compared with those reported previously for related cis-{Ru-II(NH3)(4)}(2+) species [Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845]. TD-DFT calculations on the complexes in 1-4 confirm that their lowest energy absorption bands are primarily Ru-II -> L-A MLCT in character, while Ru-II -> Tpm MLCT transitions are predicted at higher energies. DFT agrees with the Stark, but not the HRS measurements, in showing that beta(0) increases with the electron-accepting strength of L-A. The 2D nature of the chromophores is evidenced by dominant beta(xxy) tensor components.