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Abstract 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)3to 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 and31P 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.
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The reaction of primary amines with In 37 P 20 (O 2 CR) 51 is found to remove In(O 2 CR) 3 subunits from In 37 P 20 (O 2 CR) 51 . This loss of Z-type ligands coincides with structural rearrangement to alleviate core strain and passivate phosphorus atoms. This result consolidates conflicting claims that primary amines both promote and retard precursor conversion rates for InP nanocrystals.more » « less
