Register      Login
Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH FRONT

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.


References

[1]  (a) C. E. Powell, M. G. Humphrey, Coord. Chem. Rev. 2004, 248, 725.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXksF2rsrw%3D&md5=630e716aca37774e4c42ad148c739a7aCAS |
      (b) K. A. Green, M. P. Cifuentes, M. Samoc, M. G. Humphrey, Coord. Chem. Rev. 2011, 255, 2530.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) K. A. Green, M. P. Cifuentes, M. Samoc, M. G. Humphrey, Coord. Chem. Rev. 2011, 255, 2025.
         | Crossref | GoogleScholarGoogle Scholar |

[2]  (a) L. K. Myers, C. Langhoff, M. E. Thompson, J. Am. Chem. Soc. 1992, 114, 7560.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK38XltlWgs7c%3D&md5=36b54d7870151a4ba66f41c458b08806CAS |
         (b) Thompson  M. E.Chiang  W.Myers  L. K.Langhoff  C.Proc. SPIE-Int. Soc. Opt. Eng. 1991, 1497, 423.
      (c) L. K. Myers, D. M. Ho, M. E. Thompson, C. Langhoff, Polyhedron 1995, 14, 57.
         | Crossref | GoogleScholarGoogle Scholar |
         (d) Frazier  C. C.Chauchard  E. A.Cockerham  M. P.Porter  P. L.Mater. Res. Soc. Symp. Proc. 1988, 109, 323.
      (e) P. L. Porter, S. Guha, K. Kang, C. C. Frazier, Polymer 1991, 32, 1756.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) W. J. Blau, H. J. Byrne, D. J. Cardin, A. P. Davey, J. Mater. Chem. 1991, 1, 245.
         | Crossref | GoogleScholarGoogle Scholar |
      (g) A. P. Davey, H. Page, W. J. Blau, Synth. Met. 1993, 57, 3980.
         | Crossref | GoogleScholarGoogle Scholar |
      (h) S. Guha, K. Kang, P. L. Porter, J. F. Roach, D. E. Remy, F. J. Aranda, D. V. G. Rao, Opt. Lett. 1992, 17, 264.
         | Crossref | GoogleScholarGoogle Scholar |
         (i) Guha  S.Frazier  C. C.Chen  W. P.Porter  P. L.Kang  K.Proc. SPIE-Int. Soc. Opt. Eng. 1989, 1105, 14.
      (j) H. Page, W. J. Blau, A. P. Davey, X. Lou, D. J. Cardin, Synth. Met. 1994, 63, 179.
         | Crossref | GoogleScholarGoogle Scholar |
      (k) C. C. Frazier, S. Guha, W. P. Chen, M. P. Cockerham, P. L. Porter, C. H. Lee, Polymer 1987, 28, 553.
         | Crossref | GoogleScholarGoogle Scholar |
      (l) S. Guha, C. C. Frazier, P. L. Porter, K. Kang, S. E. Finberg, Opt. Lett. 1989, 14, 952.
         | Crossref | GoogleScholarGoogle Scholar |
         (m) T. B. Marder, G. Lesley, Z. Yuan, H. B. Fyfe, P. Chow, G. Stringer, I. R. Jobe, N. J. Taylor, I. D. Williams, S. K. Kurtz, in Materials for Nonlinear Optics, ACS Symposium Series 1991, Volume 455, Chapter 40, pp. 605–615 (Eds S. R. Marder, J. E. Sohn, G. D. Stucky) (American Chemical Society: Washington DC).
      (n) I. R. Whittall, M. P. Cifuentes, M. J. Costigan, M. G. Humphrey, B. W. Skelton, A. H. White, S. C. Goh, J. Organomet. Chem. 1994, 471, 193.
         | Crossref | GoogleScholarGoogle Scholar |
      (o) I. R. Whittall, M. G. Humphrey, D. C. R. Hockless, B. W. Skelton, A. H. White, Organometallics 1995, 14, 3970.
         | Crossref | GoogleScholarGoogle Scholar |
      (p) A. M. McDonagh, I. R. Whittall, M. G. Humphrey, B. W. Skelton, A. H. White, J. Organomet. Chem. 1996, 519, 229.
         | Crossref | GoogleScholarGoogle Scholar |
      (q) A. M. McDonagh, I. R. Whittall, M. G. Humphrey, D. C. R. Hockless, B. W. Skelton, A. H. White, J. Organomet. Chem. 1996, 523, 33.
         | Crossref | GoogleScholarGoogle Scholar |

[3]  (a) I. R. Whittall, M. P. Cifuentes, M. G. Humphrey, M. Samoc, B. Luther-Davies, S. Houbrechts, A. Persoons, G. A. Heath, D. Bogsanyi, Organometallics 1997, 16, 2631.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXjvVSns74%3D&md5=0f77d758a7a9d9deefd79c04dc79e664CAS |
      (b) I. R. Whittall, M. P. Cifuentes, M. G. Humphrey, B. Luther-Davies, M. Samoc, S. Houbrechts, A. Persoons, G. A. Heath, D. C. R. Hockless, J. Organomet. Chem. 1997, 549, 127.
         | Crossref | GoogleScholarGoogle Scholar |

[4]  M. G. Humphrey, Gold Bull. 2000, 33, 97.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXmsFKhuw%3D%3D&md5=1dcdc51e7af547518dec681502037d56CAS |

[5]  I. R. Whittall, M. G. Humphrey, A. Persoons, S. Houbrechts, Organometallics 1996, 15, 5738.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28Xnt1Wktro%3D&md5=fe8c6c2670c8cef24f0e7026443b25ddCAS |

[6]  M. I. Bruce, B. K. Nicholson, O. Bin Shawkataly, Inorg. Synth. 1989, 26, 324.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXhtlCrsLk%3D&md5=f8b0f89b5b4e240f673823e93eae6ac3CAS |

[7]  B. Babgi, L. Rigamonti, M. P. Cifuentes, T. C. Corkery, M. D. Randles, T. Schwich, S. Petrie, R. Stranger, A. Teshome, I. Asselberghs, K. Clays, M. Samoc, M. G. Humphrey, J. Am. Chem. Soc. 2009, 131, 10293.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXotFKntbs%3D&md5=6a4778ff33e8c5e59d371c6fda9771ecCAS |

[8]  N. Narender, K. S. K. Reddy, K. V. V. K. Mohan, S. J. Kulkarni, Tetrahedron Lett. 2007, 48, 6124.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXos1amtrs%3D&md5=6caef9f764c0c2f0647da70f09de9abdCAS |

[9]  S. Takahashi, Y. Kuroyama, K. Sonogashira, N. Hagihara, Synthesis 1980, 627.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL3MXjvVSi&md5=1f1138d1a4f788f3ca76641258350ad7CAS |

[10]  S. K. Hurst, M. P. Cifuentes, A. M. McDonagh, M. G. Humphrey, M. Samoc, B. Luther-Davies, I. Asselberghs, A. Persoons, J. Organomet. Chem. 2002, 642, 259.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XhslKr&md5=4758abb7c72185d40e4e26d4dc70acddCAS |

[11]  C. Huang, Y. Lin, P. Lin, Y. Chen, Eur. J. Org. Chem. 2006, 4510.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XhtFSqt7rO&md5=88266e00ce4e1327a2c12c1f90cf2795CAS |

[12]  (a) K. Clays, A. Persoons, Phys. Rev. Lett. 1991, 66, 2980.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXltVahtr0%3D&md5=a9709137b8b91f6c958199509706acd1CAS |
      (b) K. Clays, A. Persoons, Rev. Sci. Instrum. 1992, 63, 3285.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) K. Clays, A. Persoons, L. De Maeyer, Adv. Chem. Phys. 1994, 85, 455.

[13]  M. Stähelin, D. M. Burland, J. E. Rice, Chem. Phys. Lett. 1992, 191, 245.
         | Crossref | GoogleScholarGoogle Scholar |

[14]  M. Sheik-Bahae, A. A. Said, T. Wei, D. J. Hagan, E. W. van Stryland, IEEE J. Quantum Electron. 1990, 26, 760.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3cXltVGqs7c%3D&md5=dfa67ed790126176d14b28f6909a8e45CAS |

[15]  D. Milam, Appl. Opt. 1998, 37, 546.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXosVersA%3D%3D&md5=68dadfc6e29fff9b8ec9a8ae979632e8CAS |

[16]  (a) M. Samoc, A. Samoc, B. Luther-Davies, M. G. Humphrey, M. S. Wong, Opt. Mater. 2003, 21, 485.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XovFequrg%3D&md5=a4ad6140fa45d891c8e1039a1c748820CAS |
         (b) M. Samoc, A. Samoc, G. T. Dalton, M. P. Cifuentes, M. G. Humphrey, P. A. Fleitz, in Multiphoton Processes in Organics and Their Application 2011, Chapter 7, pp. 341–355 (Eds I. Rau, F. Kajzar) (Old City Publishing: Philadelphia, PA).

[17]  S. Di Bella, New J. Chem. 2002, 26, 495.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XjvFSqtrg%3D&md5=9c8ce6d68dbb492838148f53e60cc46cCAS |

[18]  (a) C. E. Powell, J. P. Morrall, S. A. Ward, M. P. Cifuentes, E. G. A. Notaras, M. Samoc, M. G. Humphrey, J. Am. Chem. Soc. 2004, 126, 12234.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXnsVaitro%3D&md5=fefe8074d45d99f150bcc6a908780739CAS |
      (b) M. Samoc, J. P. Morrall, G. T. Dalton, M. P. Cifuentes, M. G. Humphrey, Angew. Chem. Int. Ed. 2007, 46, 731.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) C. E. Powell, S. K. Hurst, J. P. Morrall, R. L. Roberts, M. P. Cifuentes, M. Samoc, M. G. Humphrey, Organometallics 2007, 26, 4456.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) G. T. Dalton, M. P. Cifuentes, S. Petrie, R. Stranger, M. G. Humphrey, M. Samoc, J. Am. Chem. Soc. 2007, 129, 11882.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) G. T. Dalton, M. P. Cifuentes, L. A. Watson, S. Petrie, R. Stranger, M. Samoc, M. G. Humphrey, Inorg. Chem. 2009, 48, 6534.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) R. L. Roberts, T. Schwich, T. C. Corkery, M. P. Cifuentes, K. A. Green, J. D. Farmer, P. J. Low, T. B. Marder, M. Samoc, M. G. Humphrey, Adv. Mater. 2009, 21, 2318.
         | Crossref | GoogleScholarGoogle Scholar |
      (g) K. A. Green, M. P. Cifuentes, T. C. Corkery, M. Samoc, M. G. Humphrey, Angew. Chem. Int. Ed. 2009, 48, 7867.
         | Crossref | GoogleScholarGoogle Scholar |
      (h) C. J. Jeffery, M. P. Cifuentes, A. C. Willis, M. Samoc, M. G. Humphrey, Macromol. Rapid Commun. 2010, 31, 846.
         | Crossref | GoogleScholarGoogle Scholar |
      (i) M. Samoc, T. C. Corkery, A. M. McDonagh, M. P. Cifuentes, M. G. Humphrey, Aust. J. Chem. 2011, 64, 1269.
         | Crossref | GoogleScholarGoogle Scholar |
         (j) Green  K. A.Corkery  T. C.Simpson  P. V.Cifuentes  M. P.Samoc  M.Humphrey  M. G.Macromol. Rapid Commun., in press. 10.1002/MARC.201100770