Ternary ACd(4)P(3) (A = Na, K) Nanostructures via a Hydride Solution-Phase Route.

Complex pnictides such as I-II(4)-V(3) compounds (I = alkali metal; II = divalent transition metal; V = pnictide element) display rich structural chemistry and interesting optoelectronic properties, but can be challenging to synthesize using traditional high-temperature solid-state synthesis. Soft chemistry methods can offer control over particle size, morphology, and properties. However, the synthesis of multinary pnictides from solution remains underdeveloped. Here, we report the colloidal hot-injection synthesis of ACd(4)P(3) (A = Na, K) nanostructures from their alkali metal hydrides (AH). Control studies indicate that NaCd(4)P(3) forms from monometallic Cd(0) seeds and not from binary Cd(3)P(2) nanocrystals. IR and ssNMR spectroscopy reveal tri-n-octylphosphine oxide (TOPO) and related ligands are coordinated to the ternary surface. Computational studies show that competing phases with space group symmetries R3Ì m and Cm differ by only 30 meV/formula unit, indicating that synthetic access to either of these polymorphs is possible. Our synthesis unlocks a new family of nanoscale multinary pnictide materials that could find use in optoelectronic and energy conversion devices.