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| - Phase Stabilization through Electronic Tuning: Electron-Poorer Alkali-Metal−Indium Compounds withUnprecedented In/Li Clusters
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| - Three alkali-metal−indium compounds K34In92.30Li12.70 (I), K14Na20In91.82Li13.18 (II), and K14Na20In96.30(III) (all R3̄m) have been synthesized and characterized by structural and physical property measurementsand electronic structure calculations. Novel mixed In/Li anionic icosahedra and fused icosahedra form inI and II. All three contain In28 as the first triply fused In icosahedra, which are further linked into (In28)In(In28)sandwich adducts in compounds I and II and (In28)In2(In28) in III. Stabilization of these electron-poorer phasesthrough electronic tuning occurs via two different structural (redox) perturbations, either by substitution ofcertain indium atoms in the clusters by electron-poorer lithium atoms or by the introduction of defects anddisorder in the fused cluster (III). The preferential occurrence of either substitutions or defect formation inthe clusters is consistent with extended Hückel band calculation results for both the ideal pure indiumphase and the Li-substituted equivalent. Model (ideal) and experimental EF values (based on stoichiometries)fall around a pseudogap in DOS. All three compounds are metallic according to both EHTB band calculationsand measured resistivities. The cations (A = K, Na) in all the three structures generate A136 clathrate-ΙΙtype networks with remarkably specific and transferable cation dispositions around the two types of anioniccluster units.
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