|
|||||
|
|
Aurophilic Interactions in Multi-Radical Species: Electronic-Spin and Redox Properties of Bis- and Tris-[(Nitronyl Nitroxide)-Gold(I)] Complexes with Phosphine-Ligand Scaffolds |
|
| Authors: | Sayaka Kira Takayuki Miyamae Dr. Kohei Yoshida Dr. Yuki Kanzaki Dr. Kenji Sugisaki Prof. Dr. Daisuke Shiomi Prof. Dr. Kazunobu Sato Prof. Dr. Takeji Takui Dr. Shuichi Suzuki Prof. Dr. Masatoshi Kozaki Prof. Dr. Keiji Okada |
| Affiliation: | 1. Graduate School of Science, Osaka City University Sumiyoshi-ku, Osaka, Osaka 558–8585 Japan;2. Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560–8531 Japan;3. Graduate School of Science, Osaka City University Sumiyoshi-ku, Osaka, Osaka 558–8585 Japan Osaka City University Advanced Research Institute for Natural Science and Technology (OCARINA), Osaka City University Sumiyoshi-ku, Osaka, Osaka 558–8585 Japan Deceased, April 19, 2019. |
| Abstract: | Multinuclear AuI complexes with two or three nitronyl nitroxide-2-ide radical anion and phosphine-ligand scaffolds, (NN-Au)2-1 o , (NN-Au)2-1 m , and (NN-Au)2-1 p , have been synthesized to investigate the influence of AuI−AuI (aurophilic) interactions on the properties of multispin molecular systems. The desired complexes were successfully prepared in moderate yields in a one-pot synthesis from the corresponding phosphine ligand, AuI source, parent NN, and sodium hydroxide. Among the prepared complexes, (NN-Au)2-1 o , in which an aurophilic interaction was clearly observed by crystal structure analysis, showed characteristic spin−spin interactions, electrochemical properties, and solvatochromic behavior. The results from theoretical calculations also suggested that the differences in properties between complex (NN-Au)2-1 o and the other complexes are due to intramolecular aurophilic interactions. |
| Keywords: | aurophilic interaction electronic structures redox chemistry spin-spin interaction structure elucidation |