Title: Organometallic complexes for nonlinear optics. 22. Quadratic and cubic hyperpolarizabilities of trans-bis(bidentate phosphine)ruthenium sigma-arylvinylidene and sigma-arylalkynyl complexes
Authors: Hurst, SK ×
Cifuentes, MP
Morrall, JPL
Lucas, NT
Whittall, IR
Humphrey, MG
Asselberghs, Inge
Persoons, Andre
Samoc, M
Luther-Davies, B
Willis, AC #
Issue Date: Jan-2001
Publisher: Amer chemical soc
Series Title: Organometallics vol:20 issue:22 pages:4664-4675
Abstract: The syntheses of trans-[Ru(C=CHR)Cl(pp)(2)]PF6 (pp = dppm, R = 4-C6H4C=CPh, 4-C6H4CHO, 4,4'-C6H4C drop CC6H4NO2, (E)-4,4'-C6H4CH=CHC6H4NO2, 4,4',4"-C drop CC6H4C drop CC6H4C drop CC6H4NO2; PP = dppe, R = 4-C6H4CHO, (E)-4,4'-C6H4CH=CHC6H4NO2) and trans-[Ru(C=-CR)Cl(PP)(2)] (pp = dppm, R = 4-C6H4C drop CPh, 4-C6H4CHO, 4,4-C6H4C dropC(6)H(4)NO(2), (E)4,4'-C6H4CH drop CHC6H4NO2, 4,4,4"-C drop CC6H4C drop CC6H4C drop CC6H4NO2; pp = dppe, R = 4-C6H4CHO, (E)-4,4-C6H4CH drop CHC6H4NO2) are reported, together with X-ray structural studies of trans-[Ru(C drop CR)Cl(pp)(2)] (pp = dppm, R = 4-C6H4C drop CPh; pp = dppe, R = 4-C6H4CHO, (E)-4,4'-C6H4CH drop CHC6H4NO2)- Cyclic voltammetric, linear optical, and quadratic and cubic nonlinear optical response data for these new complexes, together with the corresponding data for the previously reported trans-[Ru(C=CHR)Cl(pp)(2)]PF6 (pp = dppm, R = Ph, 4-C6H4NO2; pp = dppe, R = Ph, 4-C6H4NO2) and trans- [Ru(C drop CR)Cl(PP)(2)] (pp = dppm, R = Ph, 4-C6H4NO2, (E)-4,4'-C6H4CH drop CHC6H4NO2; pp = dppe, R = Ph, 4-C6H4NO2), are reported. Oxidation potentials for the Ru-II/III couple increase on proceeding from the neutral alkynyl complex to the analogous cationic vinylidene complex and on introduction of an acceptor group (CHO or NO2); the complexes with 4-C drop CC6H4NO2 ligands are the most difficult to oxidize. In some instances, the Ru-III/IV and Ru-I/II processes have been identified together with, where relevant, nitro-centered reduction processes. The oxidized and reduced vinylidene complexes are shown to transform electrochemically into the corresponding alkynyl complexes. Optical absorption maxima undergo a red shift upon increase of acceptor strength, replacement of the coligand dppm with dppe, and replacement of the alkynyl ligand yne linkage with an ene linkage. Proceeding from the vinylidene complex to an analogous alkynyl complex results in a small red shift in absorption maximum and a significant increase in extinction coefficient. Quadratic molecular nonlinearities by hyper-Rayleigh scattering measurements at 1064 nm increase upon introduction of ligated metal (proceeding from precursor alkyne to alkynyl or vinylidene complex), an increase in acceptor strength (introduction of CHO or NO2), alkynyl chain lengthening (in the series [4-C drop CC6H4](n)-4-NO2, proceeding from n = 1 and 2 to 3), and replacing the yne linkage with an ene linkage.
ISSN: 0276-7333
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

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