TY - JOUR
T1 - Organometallic complexes for nonlinear optics. 14. Syntheses and second-order nonlinear optical properties of ruthenium, nickel and gold σ-acetylides of 1,3,5-triethynylbenzene
T2 - X-ray crystal structures of 1-(HC ≡ C)-3,5-C6H3(trans-C ≡ CRuCl(dppm)2)2 and 1,3,5-C6H3(C ≡ CAu(PPh3))3
AU - Whittall, Ian R.
AU - Humphrey, Mark G.
AU - Houbrechts, Stephan
AU - Maes, Joachim
AU - Persoons, André
AU - Schmid, Siegbert
AU - Hockless, David C.R.
PY - 1997/10/17
Y1 - 1997/10/17
N2 - The complexes 1-(HC ≡ C)-3,5-C6H3[M]2 ([M] = trans-C ≡ CRuCl(dppm)2 (1), C ≡ CNi(PPh3)(η5-C5H5) (2)) and 1,3,5-C6H3(C ≡ CAu(PPh3))3 (3) have been prepared by extensions of well-established σ-acetylide synthetic methodologies, and 1 and 3 have been structurally characterized. Steric restrictions preclude coordination of three trans-RuCl(dppm)2 or Ni(PPh3)(η5-C5H5) moieties about the central 1,3,5-triethynylbenzene unit, a problem which the smaller Au(PPh3) group does not experience. The quadratic optical nonlinearities at 1.06 μm have been investigated by hyper-Rayleigh scattering with the C2h symmetry complexes 1 and 2 having significantly larger βHRS than their monometallic [M]C ≡ CPh ([M] = trans-RuCl(dppm)2 (4) and Ni(PPh3)(η5-C5H5) (5)) counterparts. The D3h symmetry octopolar complex 3 has a similar nonlinearity to its dipolar monometallic analogue Au(C ≡ CPh)(PPh3) (6). Complexes 1, 2 and 3 have λmax similar to 4, 5 and 6 (i.e., no loss of optical transparency is observed), but have significantly larger oscillator strengths for the important optical transitions.
AB - The complexes 1-(HC ≡ C)-3,5-C6H3[M]2 ([M] = trans-C ≡ CRuCl(dppm)2 (1), C ≡ CNi(PPh3)(η5-C5H5) (2)) and 1,3,5-C6H3(C ≡ CAu(PPh3))3 (3) have been prepared by extensions of well-established σ-acetylide synthetic methodologies, and 1 and 3 have been structurally characterized. Steric restrictions preclude coordination of three trans-RuCl(dppm)2 or Ni(PPh3)(η5-C5H5) moieties about the central 1,3,5-triethynylbenzene unit, a problem which the smaller Au(PPh3) group does not experience. The quadratic optical nonlinearities at 1.06 μm have been investigated by hyper-Rayleigh scattering with the C2h symmetry complexes 1 and 2 having significantly larger βHRS than their monometallic [M]C ≡ CPh ([M] = trans-RuCl(dppm)2 (4) and Ni(PPh3)(η5-C5H5) (5)) counterparts. The D3h symmetry octopolar complex 3 has a similar nonlinearity to its dipolar monometallic analogue Au(C ≡ CPh)(PPh3) (6). Complexes 1, 2 and 3 have λmax similar to 4, 5 and 6 (i.e., no loss of optical transparency is observed), but have significantly larger oscillator strengths for the important optical transitions.
KW - Acetylide
KW - Alkynyl
KW - Gold
KW - Nickel
KW - Nonlinear optics
KW - Ruthenium
KW - Susceptibility
UR - http://www.scopus.com/inward/record.url?scp=0031576284&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(97)00320-3
DO - 10.1016/S0022-328X(97)00320-3
M3 - Article
AN - SCOPUS:0031576284
SN - 0022-328X
VL - 544
SP - 277
EP - 283
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 2
ER -