Single-Crystal and Electronic Structure of a 1.3 nm Indium Phosphide Nanocluster

Journal of the American Chemical Society
Dylan C GaryBrandi M Cossairt

Abstract

Magic-sized nanoclusters have been implicated as mechanistically relevant intermediates in the synthesis of group III-V quantum dots. Herein we report the single-crystal X-ray diffraction structure of a carboxylate-ligated indium phosphide magic-sized nanocluster at 0.83 Å resolution. The structure of this cluster, In37P20(O2CR)51, deviates from that of known crystal phases and possesses a non-stoichiometric, charged core composed of a series of fused 6-membered rings. The cluster is completely passivated by bidentate carboxylate ligands exhibiting predominantly bridging binding modes. The absorption spectrum of the cluster shows an asymmetric line shape that is broader than what would be expected from a homogeneous sample. A combination of computational and experimental evidence suggests that the spectral line width is a result of multiple, discrete electronic transitions that couple to vibrations of the nanocrystal lattice. The product of reaction of this nanocluster with 1 equiv of water has also been structurally characterized, demonstrating site selectivity without a drastic alteration of electronic structure.

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Citations

Oct 4, 2016·Journal of the American Chemical Society·Lisi XieKlavs F Jensen
Mar 10, 2017·Inorganic Chemistry·Max R FriedfeldBrandi M Cossairt
Feb 15, 2017·Chemical Communications : Chem Comm·Jiajia Ning, Uri Banin
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