Australian Journal of Chemistry Australian Journal of Chemistry Society
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Organometallic Complexes for Non-Linear Optics. 51. Second- and Third-Order Non-Linear Optical Properties of Alkynylgold Complexes*

Adam Barlow A , Bandar Babgi A , Marek Samoc B C , T. Christopher Corkery A , Stijn van Cleuvenbergen D , Inge Asselberghs D , Koen Clays D , Marie P. Cifuentes A and Mark G. Humphrey A E
+ Author Affiliations
- Author Affiliations

A Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.

B Laser Physics Centre, Research School of Physics and Engineering, Australian National University, Canberra, ACT 0200, Australia.

C Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology, Wroclaw 50-370, Poland.

D Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200D, 3001 Leuven, Belgium.

E Corresponding author. Email: Mark.Humphrey@anu.edu.au

Australian Journal of Chemistry 65(7) 834-841 https://doi.org/10.1071/CH12054
Submitted: 30 January 2012  Accepted: 20 February 2012   Published: 16 April 2012

Abstract

The alkynes HC≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2 (4) and HC≡CC6H4-4-C≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2 (6) and gold alkynyl complexes Au{C≡CC6H2-2,5-(OEt)2-4-C≡CC6H4-4-NO2}(PPh3) (7), Au(C≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2)(PPh3) (8), and Au(C≡CC6H4-4-C≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2)(PPh3) (9) have been synthesized. The linear optical properties and quadratic optical non-linearities of 79 have been measured, the latter by hyper-Rayleigh scattering at 1064 nm, and compared with data for the previously reported complexes Au(C≡CC6H4-4-NO2)(PPh3) (10) and Au(C≡CC6H4-4-C≡CC6H4-4-NO2)(PPh3) (11). The optical absorption maximum red-shifts and the first hyperpolarizabilities increase on π-system lengthening and on introduction of electron-releasing substituents on the π-bridge ring adjacent to the metal centre. The cubic non-linear optical properties of 1,4-{(PCy3)Au(C≡C)}2C6H4 (12) and {(PCy3)Au(C≡C-4-C6H4C≡C)}6C6 (13) have been assessed by wide spectroscopic range femtosecond Z-scan studies; the maximal values of the imaginary component and the effective two-photon absorption cross-section increase markedly on proceeding from linear complex 12 to 6-fold-symmetric complex 13, an increase that is maintained when data are scaled by relative molecular weight.


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