Abstract
Herein we report the syntheses and the X-ray structure of [Cs8X27]19- (X = Cl, Br) clusters, the first binary cluster anions isolated in bulk crystal structures. They were obtained by electrostatic capture and face-directed recognition of the prenucleation [CsmCln](n-m)- clusters from water solutions, using [M4(OH)8(OH2)16]8+ (M = ZrIV or HfIV) as the counter cations. These compounds have been thoroughly characterized with a variety of techniques including vibrational spectroscopy and superionic conductivity analysis. This work not only provides structural models for a better understanding of the nucleation of binary materials but also shows that magic number binary clusters adopting a cubic lattice structure do form, in agreement with the time-honored theoretical and spectroscopic predictions.
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