TY - JOUR
T1 - Organometallic complexes for nonlinear optics
T2 - Part 23. Quadratic and cubic hyperpolarizabilities of acetylide and vinylidene complexes derived from protected and free formylphenylacetylenes
AU - Hurst, Stephanie K.
AU - Lucas, Nigel T.
AU - Cifuentes, Marie P.
AU - Humphrey, Mark G.
AU - Samoc, Marek
AU - Luther-Davies, Barry
AU - Asselberghs, Inge
AU - Van Boxel, Roel
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 supporting 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, N.T.L. was an Australian Postgraduate Awardee and M.G.H. holds an ARC Australian Senior Research Fellowship.
PY - 2001/8/10
Y1 - 2001/8/10
N2 - The acetylenes 4-HCCC6H4R [R=CH{OC(O)Me}2 (1), CHO(CH2)3O (2)], ruthenium complexes [Ru(4-CCC6H4R)(PPh3)2(η-C 5H5)] [R=CH{OC(O)Me}2 (3), CHO (4)], [Ru(n-C=CHC6H4R)Cl(dppm)2]PF6 [n=4, R=CHO(CH2)3O (7); R=CHO, n=3 (11), 2 (15)], and [Ru(n-CCC6H4R)Cl(dppm)2] [n=4, R=CHO(CH2)3O (8); n=3, R=CHO (12)], and gold complexes [Au(n-CCC6H4R)(L)] [n=4, R=CHO, L=PPh3 (5), PMe3 (6); n=4, R=CHO(CH2)3O, L=PPh3 (9), PMe3 (10); n=3, R=CHO, L=PPh3 (13), PMe3 (14)] have been prepared, and 9 characterized by a single crystal X-ray diffraction study. Electrochemical data for the ruthenium complexes reveal reversible or quasi-reversible (alkynyl complexes) or irreversible (vinylidene complexes) processes assigned to the RuII/III couple; the effect on E1/2 values of the various structural modifications across 3, 4, 7, 8, 11, 12 and 15 are discussed. The molecular quadratic and cubic optical nonlinearities of 1-15 have been determined by the hyper-Rayleigh scattering technique at 1064 nm and the Z-scan technique at 800 nm, respectively; β values increase on increasing the acceptor strength, proceeding from 3-acceptor-substituted to 4-acceptor-substituted arylalkynyl ligand, and an increasing phosphine donor strength, whereas γ values increase on increasing the number of phosphine aryl groups (i.e. increasing delocalization) proceeding from PMe3 to PPh3-containing complex.
AB - The acetylenes 4-HCCC6H4R [R=CH{OC(O)Me}2 (1), CHO(CH2)3O (2)], ruthenium complexes [Ru(4-CCC6H4R)(PPh3)2(η-C 5H5)] [R=CH{OC(O)Me}2 (3), CHO (4)], [Ru(n-C=CHC6H4R)Cl(dppm)2]PF6 [n=4, R=CHO(CH2)3O (7); R=CHO, n=3 (11), 2 (15)], and [Ru(n-CCC6H4R)Cl(dppm)2] [n=4, R=CHO(CH2)3O (8); n=3, R=CHO (12)], and gold complexes [Au(n-CCC6H4R)(L)] [n=4, R=CHO, L=PPh3 (5), PMe3 (6); n=4, R=CHO(CH2)3O, L=PPh3 (9), PMe3 (10); n=3, R=CHO, L=PPh3 (13), PMe3 (14)] have been prepared, and 9 characterized by a single crystal X-ray diffraction study. Electrochemical data for the ruthenium complexes reveal reversible or quasi-reversible (alkynyl complexes) or irreversible (vinylidene complexes) processes assigned to the RuII/III couple; the effect on E1/2 values of the various structural modifications across 3, 4, 7, 8, 11, 12 and 15 are discussed. The molecular quadratic and cubic optical nonlinearities of 1-15 have been determined by the hyper-Rayleigh scattering technique at 1064 nm and the Z-scan technique at 800 nm, respectively; β values increase on increasing the acceptor strength, proceeding from 3-acceptor-substituted to 4-acceptor-substituted arylalkynyl ligand, and an increasing phosphine donor strength, whereas γ values increase on increasing the number of phosphine aryl groups (i.e. increasing delocalization) proceeding from PMe3 to PPh3-containing complex.
KW - Acetylide
KW - Electrochemistry
KW - Gold
KW - Hyperpolarizability
KW - Ruthenium
KW - Vinylidene
KW - X-ray structure
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U2 - 10.1016/S0022-328X(01)01077-4
DO - 10.1016/S0022-328X(01)01077-4
M3 - Article
AN - SCOPUS:0012425099
SN - 0022-328X
VL - 633
SP - 114
EP - 124
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -