Rhombohedral polytypes of the layered honeycomb delafossites with optical brilliance in the visible.

We report the synthesis of the Delafossite honeycomb compounds Cu3Ni2SbO6 and Cu3Co2SbO6 via a copper topotactic reaction from the layered α-NaFeO2-like precursors Na3Ni2SbO6 and Na3Co2SbO6. The low-temperature exchange reaction exclusively produces the rhombahedral 3R polytype subcell, whereas only the hexagonal 2H polytype subcell has been made by conventional synthesis. The thus-synthesized 3R variants are visually striking; they are bright lime-green (Ni variant) and terracotta-orange (Co variant), while both of the conventionally synthesized 2H variants have a burnt-red color. The new structures are characterized by powder X-ray diffraction and Rietveld analysis as well as magnetic susceptibility, X-ray photoelectron spectroscopy (XPS), and diffuse-reflectance optical spectroscopy. Using thermogravimetric analysis, we identify a second order 3R → 2H phase transition as well as a first-order structural transition associated with rearrangement of the honeycomb stacking layers. The optical absorbance spectra of the samples show discrete edges that correlate well to their visual colors. Exposing Cu3Ni2SbO6 to O2 and heat causes the sample to change color. XPS confirms the presence of Cu(2+) in these samples, which implies that the difference in color between the polytypes is due to oxygen intercalation resulting from their different synthetic routes.