TY - JOUR
T1 - Synthesis, Characterisation of (Arene)tricarbonylchromium Complexes Linked to Cationic Fe and Ru Derivatives and Studies of First Hyperpolarisabilities by Hyper-Rayleigh Scattering
AU - Garcia, Maria Helena
AU - Royer, Sophie
AU - Robalo, Maria Paula
AU - Romão Dias, Alberto
AU - Tranchier, Jean Philippe
AU - Chavignon, René
AU - Prim, Damien
AU - Auffrant, Audrey
AU - Rose-Munch, Françoise
AU - Rose, Eric
AU - Vaissermann, Jacqueline
AU - Persoons, André
AU - Asselberghs, Inge
PY - 2003/11/7
Y1 - 2003/11/7
N2 - In order to investigate the non-linear optical properties, in particular second-order effects of binuclear organometallic complexes, a series of new cationic binuclear [MCp-(DPPE)N≡C-(spacer)-C≡C-C6H 5Cr(CO)3]+[PF6]- compounds and mononuclear precursors [N≡C-(spacer)-C≡ C-C 6H5Cr(CO)3] have been synthesised [where M = FeII or RuII; Cp = η5-C5H 5 and spacer = phenyl ring (C6H4), thiophene, (C4H2S), or bithiophene (C4H2S) 2]. The Fe or Ru organometallic π-donor fragments were linked by an extended π system to the acceptor Cr(CO)3 fragment. The effect of π back-donation involving the second Fe or Ru metal centre and the π* orbitals of the N≡C-coordinated group, was probed by the V(N≡C) stretching bands on the IR spectra and also by NMR spectroscopic data. The planarity, largely due to the π-electron resonance, found on the solid state structure of the mononuclear complex [N≡C-C 6H5-C≡C-(η6-C6H 5)Cr(CO)3] (1Cr) determined by X-ray diffraction [mono-clinic system, P21/c space group, with a = 10.326(2) Å, b = 13.209(5) Å, c = 11.799(2) Å and Z = 4] emphasises the electronic effect of this building block. The significant values of first hyperpolarisabihty β determined by hyper-Rayleigh scattering (HRS) indicate that the Fe containing compounds were more efficient on second-order non-linear optical properties than the ruthenium analogues and the parent mononuclear chromium compounds. (
AB - In order to investigate the non-linear optical properties, in particular second-order effects of binuclear organometallic complexes, a series of new cationic binuclear [MCp-(DPPE)N≡C-(spacer)-C≡C-C6H 5Cr(CO)3]+[PF6]- compounds and mononuclear precursors [N≡C-(spacer)-C≡ C-C 6H5Cr(CO)3] have been synthesised [where M = FeII or RuII; Cp = η5-C5H 5 and spacer = phenyl ring (C6H4), thiophene, (C4H2S), or bithiophene (C4H2S) 2]. The Fe or Ru organometallic π-donor fragments were linked by an extended π system to the acceptor Cr(CO)3 fragment. The effect of π back-donation involving the second Fe or Ru metal centre and the π* orbitals of the N≡C-coordinated group, was probed by the V(N≡C) stretching bands on the IR spectra and also by NMR spectroscopic data. The planarity, largely due to the π-electron resonance, found on the solid state structure of the mononuclear complex [N≡C-C 6H5-C≡C-(η6-C6H 5)Cr(CO)3] (1Cr) determined by X-ray diffraction [mono-clinic system, P21/c space group, with a = 10.326(2) Å, b = 13.209(5) Å, c = 11.799(2) Å and Z = 4] emphasises the electronic effect of this building block. The significant values of first hyperpolarisabihty β determined by hyper-Rayleigh scattering (HRS) indicate that the Fe containing compounds were more efficient on second-order non-linear optical properties than the ruthenium analogues and the parent mononuclear chromium compounds. (
KW - Arene ligands
KW - Carbonyl ligands
KW - Chromium
KW - Hyperpolarisability
KW - Iron
KW - Non-linear optics
KW - Ruthenium
U2 - 10.1002/ejic.200300190
DO - 10.1002/ejic.200300190
M3 - Article
AN - SCOPUS:0242459912
SN - 1434-1948
SP - 3895
EP - 3904
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 21
ER -