Title: | Tetranuclear Au(2)Cu(2) Clusters with Butterfly- and Planar-Shaped Metal Cores: Strong Rigidochromism Induced by Jahn-Teller Distortion in Two-Coordinated Gold(I) Centers |
Author(s): | Nayeri S; Jamali S; Jamjah A; Samouei H; |
Address: | "Department of Chemistry , Sharif University of Technology , P.O. Box 11155-3516, Tehran , Iran. Department of Chemistry , Texas A&M University , P.O. Box 30012, College Station , Texas 77842-3012 , United States" |
DOI: | 10.1021/acs.inorgchem.9b01414 |
ISSN/ISBN: | 1520-510X (Electronic) 0020-1669 (Linking) |
Abstract: | "Two tetranuclear Au(2)Cu(2) cluster complexes [Au(2)Cu(2)(mu-(PPh(2))(2)py)(2)(mu-OH)](PF(6))(3), 2, and [Au(2)Cu(2)Cl(2)(mu-(PPh(2))(2) py)(2)](OTf)(2), 4, have been prepared by the reactions of precursor complexes [Au(2)(mu-(PPh(2))(2)py)(2)](OTf)(2), 1, and [Cu(2)(mu-(PPh(2))(2)py)(2)(mu-SMe(2))(OTf)(2)], 3, with [Cu(NCCH(3))(4)]PF(6) and AuCl(SMe(2)), respectively. The crystal structures of complexes 2 and 4 were determined by X-ray crystallography, indicating a butterfly-shaped Au(2)Cu(2) metal core for 2 and a planar-shaped Au(2)Cu(2) 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" |
Notes: | "PubMed-not-MEDLINENayeri, Sara Jamali, Sirous Jamjah, Ali Samouei, Hamidreza eng 2019/09/17 Inorg Chem. 2019 Sep 16; 58(18):12122-12131. doi: 10.1021/acs.inorgchem.9b01414. Epub 2019 Sep 5" |