X-Ray structural and gas phase studies of silver(i) perfluorinated carboxylate complexes with 2,2′-bipyridyl as potential precursors for chemical vapour deposition (CVD)

Abstract

[Ag(CF(3)COO)(bpy)] (), [Ag(2)(C(2)F(5)COO)(2)(bpy)] () and [Ag(2)(C(3)F(7)COO)(2)(bpy)] () were prepared and characterized by MS-EI, (1)H, (13)C NMR, variable-temperature IR (VT-IR) spectroscopy (solid sample and evolved volatile species) and thermal analysis. Single-crystal X-ray diffraction data revealed the polymeric structure for [Ag(2)(C(2)F(5)COO)(2)(bpy)] and [Ag(6)(C(3)F(7)COO)(6)(bpy)(4)], with bridging bpy ligand, whereas for [Ag(CF(3)COO)(bpy)] the dimeric system with monodentately linked carboxylate was noted. Mass spectra analysis of () over 30-300 degrees C indicates the presence of binuclear ions [(RCOO)Ag(2)](+) as a main volatile particles, which can be transported in CVD process. VT-IR studies of gases evolved during the thermal decomposition process, demonstrate the presence of fluorocarbon species and CO(2) as the most abundant molecules. Thermal analysis of () revealed a multi-stage decomposition mechanism resulting in Ag(0) formation below 290 degrees C. Compounds were tested for silver metal spray pyrolysis and obtained layers were characterized by scanning electron microscopy (SEM-EDX) and XRD.