Tetranuclear Au2Cu2 Clusters with Butterfly- and Planar-Shaped Metal Cores: Strong Rigidochromism Induced by Jahn-Teller Distortion in Two-Coordinated Gold(I) Centers. Academic Article uri icon


  • Two tetranuclear Au2Cu2 cluster complexes [Au2Cu2(-(PPh2)2py)2(-OH)](PF6)3, 2, and [Au2Cu2Cl2(-(PPh2)2 py)2](OTf)2, 4, have been prepared by the reactions of precursor complexes [Au2(-(PPh2)2py)2](OTf)2, 1, and [Cu2(-(PPh2)2py)2(-SMe2)(OTf)2], 3, with [Cu(NCCH3)4]PF6 and AuCl(SMe2), respectively. The crystal structures of complexes 2 and 4 were determined by X-ray crystallography, indicating a butterfly-shaped Au2Cu2 metal core for 2 and a planar-shaped Au2Cu2 metal core for 4. In complex 2, the Cu atoms occupy the edge-sharing bond, while in complex 4, alternating Au and Cu atoms occupy the tetragon vertices. The optical properties of the complexes were investigated by experimental and computational methods. Although complex 2 displayed a luminescence vapochromic behavior in the presence several volatile organic compounds, complex 4 indicated only an distinguishable change in its emission color when it was exposed to vapor of hydrogen-bond donor solvents. The calculations showed that 2 undergoes an unsymmetrical distortion in its two-coordinated gold(I) centers upon excitation to the first triplet excited state. This distortion induces a large Stokes shift and a strong rigidochromism behavior that is unprecedented for two-coordinated gold(I) complexes.

published proceedings

  • Inorg Chem

author list (cited authors)

  • Nayeri, S., Jamali, S., Jamjah, A., & Samouei, H.

citation count

  • 14

complete list of authors

  • Nayeri, Sara||Jamali, Sirous||Jamjah, Ali||Samouei, Hamidreza

publication date

  • September 2019