title: Single-Crystal and Electronic Structure of a 1.3 nm Indium Phosphide Nanocluster.
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.
authors.affiliation: Department of Chemistry, University of Washington , Seattle, Washington 98195-1700, United States.
authors.forename: Dylan C
authors.initials: DC
authors.lastname: Gary
authors.affiliation: Department of Chemistry, University of Washington , Seattle, Washington 98195-1700, United States.
authors.forename: Sarah E
authors.initials: SE
authors.lastname: Flowers
authors.affiliation: Department of Chemistry, University of Washington , Seattle, Washington 98195-1700, United States.
authors.forename: Werner
authors.initials: W
authors.lastname: Kaminsky
authors.affiliation: Department of Chemistry, University of Washington , Seattle, Washington 98195-1700, United States.
authors.forename: Alessio
authors.initials: A
authors.lastname: Petrone
authors.affiliation: Department of Chemistry, University of Washington , Seattle, Washington 98195-1700, United States.
authors.forename: Xiaosong
authors.initials: X
authors.lastname: Li
authors.affiliation: Department of Chemistry, University of Washington , Seattle, Washington 98195-1700, United States.
authors.forename: Brandi M
authors.initials: BM
authors.lastname: Cossairt