TY - JOUR
T1 - Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes
AU - Hurst, Stephanie K.
AU - Cifuentes, Marie P.
AU - McDonagh, Andrew M.
AU - Humphrey, Mark G.
AU - Samoc, Marek
AU - Luther-Davies, Barry
AU - Asselberghs, Inge
AU - Persoons, André
N1 - Funding Information:
We thank the Australian Research Council (M.G.H.), the Belgian Government (Grant No. IUAP-PIV/11) (A.P.), the Fund for Scientific Research-Flanders (G.0338.98, G.0407.98) (A.P.), the K.U. Leuven (GOA/2000/03) (A.P.) for support of this work, and Johnson-Matthey Technology Centre (M.G.H.) for the generous loan of ruthenium salts. M.P.C. held an ARC Australian Postdoctoral Research Fellowship, A.M.M. held an Australian Postgraduate Award, and M.G.H. holds an ARC Australian Senior Research Fellowship.
PY - 2002
Y1 - 2002
N2 - The complexes [Au(4-CCC6H4NO2)(L)] [L=PCy3 (1), PMe3 (2)], [(L)Au(μ-4-CCRCC)Au(L)] [R=C6H4, L=PCy3 (4), PPh3 (5); R=C6H4-4-C6H4, L=PCy3 (7), PPh3 (8)], trans,trans-[RuCl(dppm)2(μ-4,4′-CCC6H4C6H4CC)RuCl(dppm)2] (11), trans-[Ru(X)(Y)(dppe)2] [X=Cl, Y=4-CCC6H4I (12), 4-CCC6H4CCSiMe3 (13); X=CCPh, 4-CCC6H4CCH (14)] and {trans-[Ru(CCPh)(dppe)2]}2(μ-4,4′-CCC6H4CCCCC6H4CC) (15) have been prepared and their electrochemical (Ru complexes) and nonlinear optical properties assessed. Electronic communication between the metal centers in 10, 11 and 15 diminishes as the π-delocalizable bridge is lengthened. Quadratic nonlinear optical (NLO) merit increases on replacing triarylphosphine by trialkylphosphine, the relative β values Au(4-CCC6H4NO2)(PPh3)<1<3 being observed. Cubic NLO values are small for the gold complexes and much larger for the ruthenium examples. Complex 15 has the largest σ2/MWt (two-photon absorption cross-section/molecular weight) value observed thus far for an organometallic complex.
AB - The complexes [Au(4-CCC6H4NO2)(L)] [L=PCy3 (1), PMe3 (2)], [(L)Au(μ-4-CCRCC)Au(L)] [R=C6H4, L=PCy3 (4), PPh3 (5); R=C6H4-4-C6H4, L=PCy3 (7), PPh3 (8)], trans,trans-[RuCl(dppm)2(μ-4,4′-CCC6H4C6H4CC)RuCl(dppm)2] (11), trans-[Ru(X)(Y)(dppe)2] [X=Cl, Y=4-CCC6H4I (12), 4-CCC6H4CCSiMe3 (13); X=CCPh, 4-CCC6H4CCH (14)] and {trans-[Ru(CCPh)(dppe)2]}2(μ-4,4′-CCC6H4CCCCC6H4CC) (15) have been prepared and their electrochemical (Ru complexes) and nonlinear optical properties assessed. Electronic communication between the metal centers in 10, 11 and 15 diminishes as the π-delocalizable bridge is lengthened. Quadratic nonlinear optical (NLO) merit increases on replacing triarylphosphine by trialkylphosphine, the relative β values Au(4-CCC6H4NO2)(PPh3)<1<3 being observed. Cubic NLO values are small for the gold complexes and much larger for the ruthenium examples. Complex 15 has the largest σ2/MWt (two-photon absorption cross-section/molecular weight) value observed thus far for an organometallic complex.
KW - Acetylide
KW - Electrochemistry
KW - Gold
KW - Hyperpolarizability
KW - Nonlinear optics
KW - Ruthenium
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U2 - 10.1016/S0022-328X(01)01281-5
DO - 10.1016/S0022-328X(01)01281-5
M3 - Article
AN - SCOPUS:0000258919
SN - 0022-328X
VL - 642
SP - 259
EP - 267
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -