Phase Discovery and Selected Synthesis of Subvalent Niobium Tellurides Using a Polytelluride Flux Strategy.

Transition metal subchalcogenides involve electron-rich metals and can facilitate an in-depth understanding of the relationships among quantum properties such as superconductivity, charge density wave, and topological band structures. However, effective experimental routes toward synthesizing transition metal subchalcogenides are still lacking, hindering the development of new quantum materials. Herein, we propose a eutectic polytelluride flux strategy as an excellent solution to address phase discovery and crystal growth in transition metal subtelluride systems. We report new phases easily and selectively synthesized using a eutectic "KTe" polytelluride flux upon adjusting the ratio of Nb metal to flux in the starting materials (K/Nb/Te = 3::4). Using a high Nb content in the solvent ( = 2 and 1), crystals of KNbTeO and KNbTe are obtained. Both subtellurides exhibit diverse Nb clusters, including face-sharing and edge-sharing Nb octahedral columns and zig-zag Nb chains. Reducing the Nb content to = 0.33 leads to the formation of a layered compound, KNbTe. This compound comprises a NbTe trigonal prism with K intercalated between the layers. Single crystals of known binary Nb tellurides can also be grown using another eutectic flux "KTe", and the obtained NbTe exhibits a new polymorphism with extra trimerization along the -axis in the Nb-Nb bonded double zig-zag cluster. Precise control over the structural dimensionality and oxidation state, combined with the facile crystal growth process, makes our synthetic strategy an efficient route to explore quantum materials in transition metal subchalcogenides.