Templated Growth of InP Nanocrystals with a Polytwistane Structure

We have synthesized InP nanocrystals of an unprecedented crystal phase at low temperature (35-100 °C) by templated growth of InP magic-sized clusters. With the addition of stoichiometric equivalents of P(SiMe₃ )₃ to the starting cluster, we demonstrate nanocrystal growth mediated through a partial dissolution and recrystallization pathway. This growth process was monitored using a combination of in situ UV/Vis and ³¹ P NMR spectroscopy, revealing the intermediacy of smaller cluster species of higher symmetry. The nanocrystals that result from this templated growth exhibit a crystal structure that is neither zincblende nor wurtzite, and instead is derived from the original cluster. This structure is best described as a 3D polytwistane phase as deduced from a combination of X-ray diffraction, Raman, and solid-state NMR spectroscopy methods.