Positions Of Metal Atoms Research Articles

Probing individual single atom electrocatalyst sites by advanced analytical scanning transmission electron microscopy

Single atom electrocatalysts (SAEs) are promising next-generation materials for promoting a variety of important reactions, such as the oxygen reduction, nitrogen reduction, and CO2 reduction reactions. While bulk characterization techniques such as X-ray absorption spectroscopy and Mössbauer spectroscopy have significantly enhanced our understanding of these catalysts, direct probing of individual single metal atom sites at the atomic scale is necessary to understand local variations in the properties of these sites and accelerate design and synthesis of improved SAEs. Aberration-corrected scanning transmission electron microscopy (STEM) has become a powerful tool for providing this type of atomic-scale information about SAE metal sites. These sites are typically unstable under the electron beam, however, which, in combination with conventional acquisition methods and detectors, has limited the type and quantity of information obtainable by spectroscopic STEM techniques. Here, we map multiple individual SAE metal sites in a nitrogen-doped carbon containing atomically dispersed Fe and Re (FeReNC) at the atomic scale by direct electron detection electron energy-loss spectroscopy (EELS). Direct electron detection provides an improved signal-to-noise ratio over conventional scintillator-based detectors and enables detection and real space localization of weak signals. In addition, we demonstrate an automated method for identification of metal atom positions, placement of the probe on these sites, and simultaneous EELS and energy dispersive X-ray spectroscopic (EDS) signal acquisition. This simultaneous acquisition of EELS and EDS provides access to the composition and bonding of a wide range of SAE metal sites. Focusing the probe directly on the metal sites also increases the relevant data acquisition rate by more than an order of magnitude over two-dimensional mapping, enabling improved statistical measurements of site properties. The versatility, sensitivity, and speed that these techniques provide enhances our ability to probe the local elemental and chemical environment of a large number of individual SAE metal site structures at the atomic scale, enabling an improved understanding of the variations in the local properties of these electrocatalysts to be gained. As a result, significantly increased information about individual metal sites will be available to future electrochemical studies through these techniques, accelerating the development of advanced SAEs.

Advanced Analytical Electron Microscopy Techniques for Probing Individual PGM-Free Catalyst Sites

Hydrogen fuel cells currently utilize expensive platinum group metal nanoparticles as catalysts [1]. To reduce the cost of catalyst materials, large efforts to develop viable platinum group metal-free (PGM-free) catalyst materials, which often consist of single transition metal atoms embedded in nitrogen-doped graphitic carbon structures, are being undertaken [2]. Given the atomic-scale nature of the metal sites in these materials, their performance and stability are highly dependent on the local coordination environment and consequently electronic structure of the sites [3]. A detailed understanding of the local elemental composition and lattice structure of individual sites, and how these properties vary between sites, is therefore needed to further develop improved PGM-free catalyst materials. While many bulk techniques are available that can provide average properties of these sites, such as Mössbauer and X-ray absorption spectroscopies, techniques with high spatial resolution are needed to measure the properties of individual sites. As a result, scanning transmission electron microscopy (STEM) combined with electron energy-loss spectroscopy (EELS) and energy-dispersive X-ray spectroscopy (EDS) has proven an invaluable tool for characterization of these materials due to its ability to probe structural and electronic properties at the atomic scale [4]. However, combined with the instability of many metal sites under the electron probe, the quantity and type of information accessible by conventional STEM instrumentation and acquisition methods is limited. To better understand the local coordination environment and electronic structure of individual sites, as well as how these properties vary site to site, new techniques and hardware are therefore needed.Here, we demonstrate advancements in STEM-EELS and -EDS that allow the quality and quantity of spectroscopic information obtained from individual sites to be significantly improved over conventional method. First, we demonstrate direct real-space mapping of metal sites by using a direct electron detector in the EELS spectrometer. This increases the data acquisition rate and signal-to-noise ratio sufficiently to map metal atom positions at the atomic scale. In addition, we show how automated metal atom position identification and subsequent probe positioning allow the rate at which metal sites are probed to be increased by another order of magnitude while simultaneously increasing the quantity of data obtained from each site. Using EELS and EDS signals acquired in parallel, this automated acquisition method enables a wide range of metal site elements to be identified, as well as the local coordination environment around the sites to be determined. Combined with electronic structure measurements of the metal atoms themselves, this technique provides significantly more information about individual sites than conventional methods. The techniques presented here are therefore poised to significantly improve our understanding of the local coordination environment and electronic structure of individual PGM-free metal sites, as well how these properties vary site to site, accelerating development of these low-cost hydrogen fuel cell catalyst materials [5].

Advanced Electron Microscopy Techniques for PGM-Free Catalyst Characterization

Hydrogen fuel cells currently rely on expensive platinum group metal nanoparticle catalysts [1]. For green hydrogen production and utilization to become widely commercially viable, the cost of the devices that produce and utilize hydrogen must be significantly reduced. Platinum group metal-free (PGM-free) catalysts have the potential to greatly reduce this cost, and materials consisting of single transition metal atoms embedded in a nitrogen-doped graphitic carbon structure have shown particular promise for use as fuel cell cathodes [2]. A better understanding of the active site properties in these materials is still needed, however, to improve their stability and design new active site structures with enhanced properties [3]. Due to the atomic-scale nature of the active sites in these materials, scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) have proven invaluable for demonstrating their atomically dispersed nature and composition [4]. Conventional STEM techniques have limited ability to correlate the local bonding environment and oxidation state of the metal atoms, for example, or track changes in the catalyst structure both during synthesis and as a result of cycling, which would provide a deeper understanding of the relationship between active site and catalyst properties.Here, we demonstrate advanced electron microscopy techniques that provide both enhanced and previously inaccessible information about PGM-free catalysts and their active sites. We show developments in automated identification of metal atom positions, which we use both to generate statistics about interatomic distances and to automatically position the STEM probe on individual atoms for EELS data acquisition. The former allows information about the presence of dual-metal site structures to be extracted, for example, and the latter allows compositional information with improved SNR to be obtained. Rapid automatic probe positioning also presents the opportunity for measuring the effect of local bonding environment on metal atom oxidation state, which cannot be obtained manually since these sites are typically unstable under the beam. In addition, we will show identical-location STEM (IL-STEM) techniques that allow the evolution of catalyst morphology and properties to be tracked at high resolution across synthesis steps and accelerated stress tests [5]. In particular, we use IL-STEM imaging and EELS to track deposition of graphitic material on the surface of a PGM-free catalyst that significantly improves the material’s durability, as well as track the change in the nanoscale graphitic carbon structure of the material as a function of electrochemical cycling. By providing access to enhanced compositional and bonding state information, as well as the ability to track properties as a material evolves, these techniques will advance our knowledge of PGM-free catalysts and enable better control over their properties in the future, accelerating wide-spread use of hydrogen fuel cells [6].

Heterostructures of two-dimensional transition metal dichalcogenides: Formation, ab initio modelling and possible applications

State-of-the-art technologies of fabrication of monolayers of transition metal dichalcogenides like MeX2, where Me = Mo, W; X = S, Se, Te, and their based heterostructures are considered. Results of theoretical modeling are analyzed and possibilities of band gap engineering by means of strains, impurities, vacancies, various layer stacking and combination of different materials are presented. Vacancies and impurities in the positions of metal atoms are shown to drastically change the band gap, even leading to an appearance of metallic properties, whereas a substitution of chalcogen atoms by isovalent atoms changes the properties not so dramatically. Possible applications of heterostuctures with tunable band gaps in transistors, light-emitting diodes, photoelectrochemical cells or photovoltaic devices are proposed and their advantages in comparison with commonly used analogues are discussed.

Electrophilic Trifluoromethylation of Dimetallofullerene Anions en Route to Air-Stable Single-Molecule Magnets with High Blocking Temperature of Magnetization.

Lanthanide dimetallofullerenes with single-electron M-M bonds are an important class of single molecular magnets and qubit candidates, but stabilization of their unique electronic and spin structure in the form of a neutral molecule requires functionalization of the fullerene cage with a single radical group. The lack of selectivity of the currently available procedure results in a complicated and tedious separation process. Here we demonstrate that electrophilic trifluoromethylation of a mixture of metallofullerene anions with Umemoto reagent II is highly selective toward M2@C80- (M = Tb, Y) anions, yielding M2@C80(CF3) monoadducts as the main reaction product. Single-crystal X-ray diffraction study proved attachment of the CF3 group to the pentagon/hexagon/hexagon junction and revealed that positions of metal atoms inside the fullerene cage in the cocrystal with NiOEP are strongly related to the position of the porphyrin moieties. Magnetic characterization of Tb2@C80(CF3) showed that it is a robust single-molecule magnet with broad magnetic hysteresis, 100 s blocking temperature of 25 K, and the relaxation barrier of 801(4) K, corresponding to the flipping of the Tb magnetic moment in the strongly ferromagnetically coupled [Tb3+-e-Tb3+] spin system.

Modulation of the electronic properties and photocatalytic performance of black phase monolayer GeSe by noble metal doping

Possible doping positions of noble metal atoms on the surface of monolayer GeSe.

QM/MM computations reveal details of the acetyl-CoA synthase catalytic center

The “open” (Aopen) and “closed” (Aclosed) A-clusters of the acteyl-CoA synthase (ACS) enzyme from Moorella thermoacetica have been studied using a combined quantum mechanical (QM)/molecular mechanical (MM) approach. Geometry optimizations of the oxidized, one- and two-electron reduced Aopen state have been carried out for the fully solvated ACS enzyme, and the CO ligand has been modeled in the reduced models. Using a combination of both αopen and αclosed protein scaffolds and the positions of metal atoms in these structures, we have been able to piece together critical parts of the catalytic cycle of ACS. We have replaced the unidentified exogenous ligand in the crystal structure with CO using both a square planar and tetrahedral proximal Ni atom. A one-electron reduced A-cluster that is characterized by a proximal Ni atom in a tetrahedral coordination pattern observed in both the Aopen (lower occupancy proximal Ni) and Aclosed (proximal Zn atom) geometries with three cysteine thiolates and a modeled CO ligand demonstrates excellent agreement with the crystal structure atomic positions, particularly with the displacement of the side chain ring of Phe512 which appears to serve as a structural gate for ligand binding. The QM/MM optimized geometry of the A-cluster of ACS with an uncoordinated, oxidized proximal nickel atom in a square planar geometry demonstrates poor agreement with the atomic coordinates taken from the crystal structure. Based on these calculations, we conclude that the square planar proximal nickel coordination that has been captured in the Aopen structure does not correspond to the ligand-free, oxidized [Fe4S4]2+ − Nip2+ − Nid2+ state. Overall, these computations shed further light on the mechanistic details of protein conformational changes and electronic transitions involved in the ACS catalytic cycle.

Magnetic Properties of Metal–Organic Coordination Networks Based on 3d Transition Metal Atoms

The magnetic anisotropy and exchange coupling between spins localized at the positions of 3d transition metal atoms forming two-dimensional metal–organic coordination networks (MOCNs) grown on a Au(111) metal surface are studied. In particular, we consider MOCNs made of Ni or Mn metal centers linked by 7,7,8,8-tetracyanoquinodimethane (TCNQ) organic ligands, which form rectangular networks with 1:1 stoichiometry. Based on the analysis of X-ray magnetic circular dichroism (XMCD) data taken at T = 2.5 K, we find that Ni atoms in the Ni–TCNQ MOCNs are coupled ferromagnetically and do not show any significant magnetic anisotropy, while Mn atoms in the Mn–TCNQ MOCNs are coupled antiferromagnetically and do show a weak magnetic anisotropy with in-plane magnetization. We explain these observations using both a model Hamiltonian based on mean-field Weiss theory and density functional theory calculations that include spin–orbit coupling. Our main conclusion is that the antiferromagnetic coupling between Mn spins and the in-plane magnetization of the Mn spins can be explained by neglecting effects due to the presence of the Au(111) surface, while for Ni–TCNQ the metal surface plays a role in determining the absence of magnetic anisotropy in the system.

Interaction of ZrMo2 with hydrogen at high pressure

The interaction of hydrogen with ZrMo2 intermetallic compound at pressure up to 2500 bars has been studied. In ZrMo2–H2 system desorption isotherms were measured and thermodynamic parameters of hydride phase decomposition were calculated. The structure of ZrMo2D4.0 deuteride has been investigated by X-ray and neutron diffraction methods. It was revealed that ordering of deuterium in the cubic lattice of ZrMo2 led to the formation of superstructure with tetragonal lattice. The occupancy of the positions of deuterium and metal atoms was determined.

Synthesis and Crystal Structure of (1,3‐Diammoniumpropane)3[V4W9O40]·H2O

AbstractThe new compound (1,3‐diammoniumpropane)3[V4W9O40]·H2O was synthesized under solvothermal conditions. The main structural motif is a vanadium rich Keggin anion. The central tetrahedron is solely occupied by VV, while the remaining metal atom positions are statistically occupied by VV and WVI. Between the anion and the diprotonated amine molecules a pronounced hydrogen bond network is observed. Upon heating the compound decomposes in three steps.

Modelling the metal atom positions of the Photosystem II water oxidising complex: a density functional theory appraisal of the 1.9 Å resolution crystal structure

Density functional theory (DFT) calculations are reported for a set of model compounds intended to represent the structure of the Photosystem II (PSII) water oxidising complex (WOC) as determined by the recent 1.9 Å resolution single crystal X-ray diffraction (XRD) study of Umena et al. In contrast with several other theoretical studies addressing this structure, we find that it is not necessary to invoke photoreduction of the crystalline sample below the S(1)'resting state' in order to rationalise the observed WOC geometry. Our results are consistent with crystallised PSII in the S(1) state, with S(1) corresponding to either (Mn(III))(4) or (Mn(III))(2)(Mn(IV))(2) as required by the two competing paradigms for the WOC oxidation state pattern. Of these two paradigms, the 'low-oxidation-state' paradigm provides a better match for the crystal structure, with the comparatively long Mn(2)-Mn(3) distance in particular proving difficult to reconcile with the 'high-oxidation-state' model. Best agreement with the set of metal-metal distances is obtained with a S(1) model featuring μ-O, μ-OH bridging between Mn(3) and Mn(4) and deprotonation of one water ligand on Mn(4). Theoretical modelling of the 1.9 Å structure is an important step in assessing the validity of this recent crystal structure, with implications for our understanding of the mechanism of water oxidation by PSII.

Towards full-structure determination of bimetallic nanoparticles with an aberration-corrected electron microscope

To fully understand the properties of functional nanostructures such as catalytic nanoclusters, it is necessary to know the positions of all the atoms in the nanostructure. The catalytic properties of metal nanoclusters can often be improved by the addition of a second metal, but little is known about the role of the different metals in these bimetallic catalysts, or about their interactions with each other and the support material. Here we show that aberration-corrected scanning transmission electron microscopy of supported rhodium-iridium clusters, combined with dynamic multislice image simulations, can identify individual atoms, map the full structure, and determine changes in the positions of metal atoms in sequential images. This approach could help in the development of new and improved catalysts and other functional nanostructures.

Hydration Preferences for Mn4Ca Cluster Models of Photosystem II: Location of Potential Substrate–Water Binding Sites

Density functional theory calculations are reported on a set of three model structures of the Mn(4)Ca cluster in the water-oxidizing complex of Photosystem II (PSII), which share the structural formula [CaMn(4)C(9)H(10)N(2)O(16)](q+)·(H(2)O)(n) (q=-1, 0, 1, 2, 3; n=0-7). In these calculations we have explored the preferred hydration sites of the Mn(4)Ca cluster across five overall oxidation states (S(0) to S(4)) and all feasible magnetic-coupling arrangements to identify the most likely substrate-water binding sites. We have also explored charge-compensated structures in which the overall charge on the cluster is maintained at q=0 or +1, which is consistent with the experimental data on sequential proton loss in the real system. The three model structures have skeletal arrangements that are strongly reminiscent, in their relative metal-atom positions, of the 2.9-, 3.7-, and 3.5 Å-resolution crystal structures, respectively, whereas the charge states encompassed in our study correspond to an assignment of (Mn(III))(3)Mn(II) for S(0) and up to (Mn(IV))(3)Mn(III) for S(4). The three models differ principally in terms of the spatial relationship between one Mn (Mn(4)) and a generally robust Mn(3)Ca tetrahedron that contains Mn(1), Mn(2), and Mn(3). Oxidation-state distributions across the four manganese atoms, in most of the explored charge states, are dependent on details of the cluster geometry, on the extent of assumed hydration of the clusters, and in some instances on the imposed magnetic-coupling between adjacent Mn atoms. The strongest water-binding sites are generally those on Mn(4) and Ca. However, one structure type displays a high-affinity binding site between Ca and Mn(3), the S-state-dependent binding-energy pattern of which is most consistent with the substrate water-exchange kinetics observed in functional PSII. This structure type also permits another water molecule to access the cluster in a manner consistent with the substrate-water interaction with the Mn cluster, seen in electron spin-echo envelope modulation (ESEEM) studies of the functional enzyme in the S(0) and S(2) states. It also rationalizes the significant differences in hydrogen-bonding interactions of the substrate water observed in the FTIR measurements of the S(1) and S(2) states. We suggest that these two water-binding sites, which are molecularly close, model the actual substrate-binding sites in the enzyme.

Crystals in Which Some Metal Atoms are More Equal Than Others: Inequalities From Crystal Packing and Their Spectroscopic/Magnetic Consequences

Crystal structures of the heterometallic compounds CrCrFe(dpa)(4)Cl(2) (1), CrCrMn(dpa)(4)Cl(2) (2), and MoMoMn(dpa)(4)Cl(2) (3) (dpa = 2,2'-dipyridylamide) show disorder in the metal atom positions such that the linear M(A)[quadruple bond]M(A)···M(B) array for a given molecule in the crystal is oriented in one of two opposing directions. Despite the fact that the direct coordination sphere of the metals in the two crystallographically independent orientations is identical, subtle differences in some metal-ligand bond distances are observed in 1 and 3 due to differences in the orientation of a solvent molecule of crystallization. The Fe(II) and Mn(II) ions serve as sensitive local spectroscopic probes that have been interrogated by Mössbauer spectroscopy and high-field EPR spectroscopy, respectively. The subtle differences in the two independent Fe and Mn sites in 1 and 3 unexpectedly give rise to unusually large differences in the measured Fe quadrupole splitting (ΔE(Q)) in 1 and Mn zero-field splitting (D) in 3. Variable-temperature/single-crystal EPR spectroscopy has allowed us to determine that the temperature-dependent D tensors in 3 are oriented along the metal-metal axis and that they show significantly different dynamic behavior with temperature. The differences in ΔE(Q) and D are reproduced by density functional calculations on truncated models for 1 and 3 that lack the quadruply bonded M(A)[quadruple bond]M(A) groups, though the magnitude of the calculated effect is not as large as that observed experimentally. We suggest that the large observed differences in ΔE(Q) and D for the individual sites could be due to the influence of the strong diamagnetic anisotropy of the quadruply bonded M[quadruple bond]M unit.

IMAGING SINGLE ATOMS IN ZEOLITES

THE POSITIONS of individual metal atoms and nanoscale metal clusters anchored within the pores of zeolite crystals have, for the first time, been pinpointed with atomic-scale resolution by using an advanced electron microscopy method, according to researchers in California who conducted the study ( Nat. Nanotechnol., DOI: 10.1038/nnano.2010.92). The imaging technique may provide a new way to study porous industrial catalysts and determine the mechanisms by which they change with use. Zeolites are nanoporous crystalline aluminosilicates that are widely used as catalysts in petroleum refining. Researchers have typically depended upon X-ray methods and NMR spectroscopy to analyze the structures of zeolites and deduce how molecules interact with them during reactions. But those methods provide averaged structural values and only limited information about catalytically active metal atoms dispersed inside zeolite pores. To zoom in on those atoms directly, a research team at the University of California, Davis, ...

Structural, Magnetic Coupling and Oxidation State Trends in Models of the CaMn4 Cluster in Photosystem II

Density functional theory calculations are reported on a set of isomeric structures I, II and III that share the structural formula [CaMn4C9H10N2O16]q+.(H2O)3 (q= -1, 0, 1, 2, 3). Species I has a skeletal structure, which has been previously identified as a close match to the ligated CaMn4 cluster in Photosystem II, as characterized in the most recent 3.0 angstroms crystal structure. Structures II and III are rearrangements of I, which largely retain that model's bridging ligand framework, but feature metal atom positions broadly consistent with, respectively, the earlier 3.5 and 3.2 angstroms crystal structures for the Photosystem II water-oxidising complex (WOC). Our study explores the influence of the cluster charge state (and hence S state) on several important properties of the model structures; including the relative energies of the three models, their interconversion, trends in the individual Mn oxidation states, preferred hydration sites and favoured modes of magnetic coupling between the manganese atoms. We find that, for several of the explored cluster charge states, modest differences in the bridging-ligand geometry exert a powerful influence over the individual manganese oxidation states, but throughout these states the robustness of the tetrahedron formed by the Ca and three of the Mn atoms remains a significant feature and contrasts with the positional flexibility of the fourth Mn atom. Although structure I is lowest in energy for most S states, the energy differences between structures for a given S state are not large. Overall, structure II provides a better match for the EXAFS derived metal-metal distance parameters for the earlier S states (S0 to S2), but not for S3 in which a significant structural change is observed experimentally. In this S state structure III provides a closer fit. The implications of these results, for the possible action of the WOC, are discussed.

A polymeric chain formed by bicapped pseudo-Keggin polyoxometalate and [Ni(en)2]2+ complexes: synthesis, structure and catalytic properties of {[H3PMo8V6O46][Ni(en)2]} · 2[Ni(en)2] · 5H2O

A new compound {[H3PMo8V6O46][Ni(en)2]} · 2[Ni(en)2] · 5H2O with a polymeric chain structure was hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR and TG. The molybdovanadophosphate cluster anion is a bicapped ‘pseudo-Keggin’ structure, in which two vanadium atoms are located at two ‘capping’ metal atom positions, another four vanadium atoms and eight molybdenum atoms are arranged as phosphorus-centered alternate layers of molybdenum and vanadium oxides. The title compound exhibits high catalytic activity for selective oxidation of benzyl alcohol to benzaldehyde. The influence of catalyst amount, the ratio, H2O2/C6H5CH2OH, reaction time and catalyst lifetime on the catalytic activity was studied.

Bridge Over Troubled Water: Resolving the Competing Photosystem II Crystal Structures

Density functional theory (DFT) calculations, at the Becke-Perdew/TZP level of theory, were used to investigate a set of CaMn(4)-containing clusters that model the active site of the water-oxidizing complex (WOC) of photosystem II (PSII). Metal-atom positions for three representative isomeric clusters of the formula [CaMn(4)C(9)N(2)O(16)H(10)](+)4 H(2)O are in good agreement with the disparate Mn(4) geometries of the three most recent X-ray crystal structures. Remarkably, interconversion between these three isomeric clusters is found to be facile, resulting from subtle changes in the coordination environment around the CaMn(4) centre. This result provides a clear rationalisation of the marked differences in reported crystal structures. Recent concerns have been raised regarding the opportunity for X-ray-damage-induced distortion of the metal-containing active centre during crystallographic analysis. Our calculations suggest that an even greater problem may be presented by the apparent fluxionality of the CaMn(4) skeleton within the active centre. Structural rearrangement may well precede crystallographic analysis, for example by the preferential "freezing-out" of one of several near-isoenergetic structures during the workup for crystallisation. This prospect, which our calculations cannot exclude, highlights the difficulties that will continue to be faced by experimentalists seeking unambiguous structural information on the WOC's active site.

Novel compounds Sn 20Zn 4P 22− vI 8 ( [formula omitted]), Sn 17Zn 7P 22I 8, and Sn 17Zn 7P 22Br 8: Synthesis, properties, and special features of their clathrate-like crystal structures

Tin–zinc pnictidehalides Sn 20Zn 4P 22− v I 8 ( v = 1.2 ), Sn 17Zn 7P 22I 8, and Sn 17Zn 7P 22Br 8 have been prepared as single-phase samples by a standard ampoule procedure. The compounds are isotypic and possess the structure of type-I gas hydrate (clathrate-I type). They all crystallize in the cubic space group Pm 3 ¯ n (no. 223) with the unit cell parameters a = 10.883 ( 2 ) Å (Sn 20Zn 4P 22− v I 8), a = 10.8458 ( 3 ) Å (Sn 17Zn 7P 22I 8), a = 10.7449 ( 2 ) Å (Sn 17Zn 7P 22Br 8), and Z = 1 . The crystal structures of all compounds have been solved from single-crystal X-ray diffraction data sets and refined to R = 0.032 (Sn 20Zn 4P 22− v I 8), R = 0.027 (Sn 17Zn 7P 22I 8), and R = 0.020 (Sn 17Zn 7P 22Br 8). In all structures tin, zinc, and phosphorus atoms form the clathrate-I framework while the guest halogen atoms are encapsulated in the cavities of the framework. The compositions of the synthesized compounds are in agreement with those predicted by using the Zintl–Klemm concept. Sn 20Zn 4P 22− v I 8 contains two partially filled metal sites and vacancies in one of the phosphorus sites and can be formulated as Sn 20Zn 4P 20.8□ 1.2I 8 (or Sn 20Zn 4P 22−1.2I 8). Sn 17Zn 7P 22I 8 and Sn 17Zn 7P 22Br 8 are vacancy-free and reveal three partially filled positions of metal atoms. Thus, Sn 17Zn 7P 22 X 8 and Sn 20Zn 4P 20.8□ 1.2I 8, being the limiting and the intermediate compositions, respectively, of the solid solutions of a general formula Sn 24− n Zn n P 22− v X 8 ( v = ( 14 − 2 n ) / 5 , X=Br, I), show different mechanisms of the structural stabilization. The 119Sn Mössbauer together with the 31P and 119Sn NMR spectra confirm the local environment of tin and phosphorus atoms in the structures of Sn 17Zn 7P 22I 8 and Sn 17Zn 7P 22Br 8. The compounds Sn 17Zn 7P 22I 8 and Sn 17Zn 7P 22Br 8 display diamagnetic and semiconducting behavior. The heat capacity has been measured for Sn 17Zn 7P 22I 8 in a temperature range of 6 K to 400 K. No low-temperature phase transitions have been detected in the measurements.

Recent progress in the studies of endohedral metallofullerenes

This overview presents the recent progress in the area of endohedral metallofullerenes in the past several years. The important results have been summarized as follows: (1) Many metals including Group 3 metals, most of the lanthanide series elements, and Group 2 metals have been encapsulated into a fullerene cage to form mono-, di-, and trimetallofullerenes by using the arc-evaporation technique. (2) Some endohedral metallofullerenes such as Group 3 metals, most of the lanthanide series elements, Group 2 metals, and some of their isomers have been successfully isolated and purified by a two-step or several-step HPLC technique. By using high-temperature and high-pressure extraction with pyridine, Ln@C 80, Ln@C 82, and Ln 2@C 80 for most rare-earth metals have been selectively extracted in high yield (about 1% of the raw soot) from fullerenes and other size metallofullerenes. (3) The endohedral nature of metallofullerenes such as Y@C 82, Sc 2@C 84, and Sc@C 82 has been finally confirmed by synchrotron X-ray powder diffraction. The symmetries and the structures of metallofullerenes such as Ca@C 82(III), La 2@C 80( I h ), Sc 2@C 84( D 2 d ), and Sc 2@C 84( C s ) have been confirmed by NMR measurements. (4) The information on the electronic structures and properties of endohedral metallofullerenes has been obtained by various spectrometric means such as EPR, UV–vis–NIR, XPS, CV. It is generally accepted that three-electron transfer is favorable when M=Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu but Sc, Eu, Sm, Yb, Tm, Ca, Sr, Ba prefer to donate two electrons to the fullerene cages. (5) Several chemical reactions of endohedral metallofullerenes have been reported in which reagents are disilacyclopropane, digermacyclopropane, diphenyldiazomethane, and trifluoroacetic acid. (6) Mass spectrometry provided the crucial evidence that led to the discovery of metallofullerenes in 1985 and has always played a key role in their identification and characterization. Ion-mobility measurements of gas-phase ions have obtained the information of structures and the formation mechanism of endohedral metallofullerenes. (7) Theoretical calculations on the endohedral metallofullerenes have made an important contribution to the studies on the symmetry of the cage, the position of metal atom(s) inside the cage, the number of electronic transfer between metal atom(s) and fullerene cage, etc.