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Organometallic Complexes for Non-linear Optics. 49. * Third-Order Non-linear Optical Spectral Dependence Studies of Arylalkynylruthenium Dendrimers
Marek
Samoc A B D,
T. Christopher
Corkery C,
Andrew M.
McDonagh C,
Marie P.
Cifuentes C and
Mark G.
Humphrey C D
A
Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology, Wroclaw 50-370, Poland.
B
Laser Physics Centre, Research School of Physics and Engineering, Australian National University, Canberra, ACT 0200, Australia.
C
Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
D
Corresponding authors. Email: marek.samoc@pwr.wroc.pl; Mark.Humphrey@anu.edu.au
Australian Journal of Chemistry
64(9)
1269-1273 http://dx.doi.org/10.1071/CH11191
Submitted: 8 May 2011 Accepted: 5 July 2011 Published:
16
September
2011
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Abstract
The cubic hyperpolarizabilities of 1,3,5-(trans-[RuCl(dppe)2(C≡CC6H4-4-C≡C)])3C6H3 (1), 1,3,5-(trans-[Ru(C≡CPh)(dppe)2(C≡CC6H4-4-C≡C)])3C6H3 (2), 1,3,5-(trans-[Ru(C≡CC6H4-4-NO2)(dppe)2(C≡CC6H4-4-C≡C)])3C6H3 (3), 1,3,5-{trans-[Ru(C≡C-3,5-(trans-[Ru(C≡CPh)(dppe)2(C≡CC6H4-4-C≡C)])2C6H3)(dppe)2(C≡CC6H4-4-C≡C)]}3C6H3 (4), and 1,3,5-{trans-[Ru(C≡C-3,5-(trans-[Ru(C≡CC6H4-4-NO2)(dppe)2(C≡CC6H4-4-C≡C)])2C6H3)(dppe)2(C≡CC6H4-4-C≡C)]}3C6H3 (5) have been assessed over the spectral range 520–1600 nm using the Z-scan technique and ~150 fs pulses. All complexes exhibit negative values of γreal (corresponding to self-defocusing behaviour) and significant positive values of γimag (corresponding to two-photon absorption) at short wavelengths (up to 1000 nm). The maximal values of γreal and γimag increase in magnitude on dendrimer generation increase (proceeding from 2 to 4 or 3 to 5). The open-aperture Z-scan results have been used to confirm and contrast the two-photon (2PA) and three-photon absorption (3PA) behaviour of 1–5, the data being consistent with the existence of 2PA at the short wavelength range, but with significant 3PA at longer wavelengths for 1–3 and 5, a record 3PA coefficient for an inorganic complex for 5 at 1180 nm, and appreciable 3PA at the telecommunications wavelength of 1300 nm. 
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