Dinuclear Gold(I) Chloride Complexes with Diarsine Ligands. Issue 3 (16th November 2020)

• Record Type: Journal Article
• Authors: Kobayashi, Ryosuke; Fujii, Toshiki; Imoto, Hiroaki; Naka, Kensuke
• Is Part Of: European journal of inorganic chemistry. Issue 3(2021)
• Page Start: 217
• Page End: 222
• Publication Date: 2020-11-16
• Subjects: Diarsine ligands -- Gold -- Aurophilicity -- Mechanochromic luminescence -- Thermochromic luminescence; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202000810
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Recently, we have developed synthetic methods for preparing diarsenic ligands. Herein, dinuclear gold(I) chloride complexes with various kinds of diarsenic ligands [Au2 Cl2 (diars)] were synthesized (diars = dpae, dpap, dpab, cis ‐dpav, trans ‐dpav, dpapz, and dpaq). X‐ray crystallography revealed that they can form intra‐ or intermolecular aurophilic interactions depending on the ligand structure except for dpab. Crystal polymorphs of Au2 Cl2 (dpae) and Au2 Cl2 (dpap) were observed because of the flexible alkylene linkers of the diarsine ligand. The emission behaviors of the complexes were drastically changed by the ligands, which should affect the energy barrier for internal conversion from the intraligand excitation state to the halide‐to‐ligand charge transfer one. Some of the complexes accordingly showed luminescent mechanochromism and/or thermochromism. Abstract : Dinuclear gold(I) chloride (AuCl) diarsine complexes were prepared by practical synthetic methods. The obtained AuCl complexes formed intra‐ and/or intermolecular aurophilic interactions depending on the ligands, and some of them showed crystalline polymorphism. The luminescence properties were varied by external stimuli such as grinding and cooling. This is the first systematic study on AuCl complexes with arsenic ligands.