Racioppi Stefano, Andrzejewski Michał, Colombo Valentina, Sironi Angelo, Macchi Piero
Department of Chemistry and Biochemistry , University of Bern , Freiestrasse 3 , Bern CH-3012 , Switzerland.
Dipartimento di Chimica , Università degli Studi di Milano , Via Golgi, 19 , 20133 Milano , Italy.
Inorg Chem. 2020 Feb 17;59(4):2223-2227. doi: 10.1021/acs.inorgchem.9b02852. Epub 2020 Jan 30.
Two isostructural coordination polymers with coinage metal(I) cations were compressed with the purpose of testing interactions between chains, which may trigger metallophilic interactions or otherwise expand the metal coordination. DFT calculations and X-ray diffraction studies reveal an extraordinary difference between Ag(I) and Cu(I) in homologous compounds. Argentophilic interactions are favored by a mild compression, and at = 7.94 GPa, the Ag-Ag distance matches the value of metallic silver. On the other hand, no cuprophilic interaction is activated even by compression up to 8 GPa, and Cu-Cu distances remain outside the van der Waals spheres.
为了测试链间相互作用(这可能引发亲金属相互作用或以其他方式扩展金属配位),对两种含货币金属(I)阳离子的同构配位聚合物进行了压缩。密度泛函理论(DFT)计算和X射线衍射研究揭示了同源化合物中Ag(I)和Cu(I)之间的显著差异。适度压缩有利于亲银相互作用,在7.94 GPa时,Ag-Ag距离与金属银的值匹配。另一方面,即使压缩至8 GPa也未激活亲铜相互作用,Cu-Cu距离仍保持在范德华球之外。