Electronic structure and bonding in endohedral Zintl clusters

Abstract

Despite many different views on the bonding in endohedral Zintl clusters, the relationship between their valence electron count and their structure and bonding patterns is much more uniform than previously anticipated, as highlighted in this article.

Optical absorption and shape transition in neutral SnNclusters withN≤ 40: a photodissociation spectroscopy and electric beam deflection study

“…36,[72][73][74][75][76][77] Also, the icosahedral stannaspherene cluster Sn 12 2À which was found by photoelectron spectroscopy [78][79][80][81] has acquired huge interest due to being the scaffold for paramagnetic superatoms [82][83][84] as well as its relation to Zintl ions and (inter-)metalloid compounds. [85][86][87][88][89][90][91][92][93][94][95][96][97][98] Neutral clusters, however, are more difficult to probe experimentally. There are only two kinds of studies addressing the geometry discrimination of neutral tin clusters, one which measures the formation energies of tin cluster distributions consisting of hundreds of atoms calorimetrically 99,100 and one which focuses on the structure elucidation of Sn N clusters with N = 6-20 based on measuring the Stark effect in combination with photoionization and quantum chemical calculations.…”

Observation of Anomalously High Seebeck Coefficients in the Family of Zintl Phase Semiconductors Ca10RECdSb9 (RE = Rare-Earth Metal)

“…The Zintl phases (which fall at the border of the typical valence-precise compounds and the intermetallic compounds) , have continued to provide us with numerous research opportunities to tune the electronic, optoelectronic, and transport properties that may be beneficial for thermoelectric, infrared nonlinear optics, and photovoltaic applications. − The material landscapes are rich, and discoveries of unexpected chemistry and physics abound . For thermoelectric applications, in particular, materials with narrow band gaps are sought after since they provide high carrier mobility and electrical conductivity, which are desired for developing efficient thermoelectrics. , Also, the amenability of Zintl materials to complex atomic bonding and heavy atomic site disorder that can provide for effective anharmonic phonon scatterings are also crucial features that can be harnessed toward achieving ultralow thermal conductivity .…”

Geometries, electronic structures, and bonding properties of endohedral Group‐14 Zintl clusters TM@E10 (TM = Fe, Co, Ni; E = Ge, Sn, Pb)

“…The Zintl phases are intermetallic compounds consisting of electropositive alkali or alkaline earth elements or lanthanides and electronegative p-block elements. [1][2][3][4] When Group 14 elements play as p-block elements in Zintl phases, soluble molecular Zintl anionic clusters form. 5 Those Zintl clusters [E n ] nÀ (E = Si, Ge, Sn, Pb) attract wide research interests not only because their simple beauty provides ideal models for studying the chemical bonding within clusters but also since they are outstanding building blocks for cluster-assembled nanomaterials with potential physical and chemical properties.…”

“…The Zintl phases are intermetallic compounds consisting of electropositive alkali or alkaline earth elements or lanthanides and electronegative p‐block elements 1–4 . When Group 14 elements play as p‐block elements in Zintl phases, soluble molecular Zintl anionic clusters form 5 .…”