Molecular Co(II) and Co(III) Heteroarylalkenolates as Efficient Precursors for Chemical Vapor Deposition of Co3O4 Nanowires

Abstract

Two new cobalt precursors, Co(II)(PyCHCOCF3)2(DMAP)2 (1) and Co(III)(PyCHCOCF3)3 (2), based on Co(II) and Co(III) centers were synthesized using a redox active ligand system. The different chemical configurations of 1 and 2 and differential valence states of cobalt were confirmed by crystal structure determination and comprehensive analytical studies. Whereas 1 could not be studied by NMR due to the paramagnetic nature of the central atom, 2 was unambiguously characterized by multinuclear 1D and 2D NMR experiments in solution. Both compounds are efficient precursors for catalyst-free growth of Co3O4 nanowires on Si and Al2O3 substrates by a chemical vapor deposition process. The different valence states of cobalt species influenced their chemical decomposition pathways in the gas phase; for instance, 1 was partially oxidized (Co(2+) → Co(3+)), and 2 underwent reduction (Co(3+) → Co(2+)) to form pure cobaltite in both cases that verified the metal-ligand redox interplay. Co3O4 nanowires with nanometric diameters (50-100 nm) were obtained irrespective of the chosen cobalt precursor. Investigations on the humidity sensing behavior of CVD deposits demonstrated their potential as promising sensor materials.