Gas-phase synthesis and deposition of metal–bipyridine complex [M–bpy1–2]+ (M = Ag, Cu). Issue 30 (27th July 2021)

• Record Type: Journal Article
• Authors: Guo, Mengdi; Huang, Benben; Yi, Qiuhao; Luo, Zhixun
• Is Part Of: Physical chemistry chemical physics. Volume 23:Issue 30(2021)
• Page Start: 16334
• Page End: 16340
• Publication Date: 2021-07-27
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d1cp02399c
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Small Ag n + and Cu n + clusters react with 2, 2′-bipyridine in the gas-phase giving rise to the production of [M–bpy1–2 ] + (M = Ag, Cu). Abstract : Controllable synthesis of organometallic clusters in the gas phase is a topic of reasonable interest with precisely tunable properties depending on sizes, compositions, and intra-cluster charge-transfer interactions. Here, we have prepared small Ag n + and Cu n + clusters by using a customized magnetron sputtering (MagS) source and observed the gas-phase reactions with 2, 2′-bipyridine. It is found that the small silver and copper clusters readily react with bipyridine and form products of [M–bpy1–2 ] + (M = Ag, Cu). Quantum chemistry calculations reveal that the bipyridine in both [Ag–bpy1–2 ] + and [Cu–bpy1–2 ] + takes on cis -conformation with altered N–C–C–N dihedral angles, which is in contrast to the trans -conformation of a free 2, 2′-bipyridine molecule itself. In order to unveil the principle of conformational transition, we have fully studied the interactions between the nitrogen atoms of bipyridine and the cationic Ag + and Cu +, calculated the donor–acceptor orbital overlaps, and analyzed the correlation of their frontier molecular orbital energy levels. Furthermore, by using a soft-landing strategy, we have managed to deposit the [Cu–bpy2 ] + complex onto the glass substrates coated with Ag nanoparticles, and recorded the surface-enhanced Raman scattering spectra.