Post-transition Elements Research Articles

Geochemistry of the Turonian-Coniacian strata: New insight into paleoenvironmental conditions of the Tethys, Eastern Pontides, NE Türkiye

The eastern part of the Sakarya Zone, known as the Eastern Pontides, is represented by a south-facing carbonate platform during the Late Jurassic-Early Cretaceous. The shallow marine carbonate sedimentation is masked by hemipelagic sedimentation during the Turonian to Coniacian. The Turonian-Coniacian strata are widely exposed in the Gümüşhane area. In this study, we present new microfacies and geochemical data that can provide new insights into the palaeo-oceanic conditions during the time of their deposition.These strata consist of yellow to gray, thick-bedded, graded calcarenites, calcilutite, pelagic limestone, and monogenic conglomerates. The dominant components are carbonate fragments, including dolomites and limestone, as well as allochthonous bioclasts. Volcanic rock fragments, quartz, cherts, and glauconites are also present, with their abundance varying along the section. The micritic component and planktonic fauna exhibit an increasing abundance in the upward direction, indicating a gradual deepening of the depositional environment. Hence, the analyzed samples can be interpreted as transgressive series deposited on slopes or the deep shelf basin.Furthermore, these strata exhibit distinct V/(V+Ni) and Ni/Co ratios without a notable negative Ce anomaly, suggesting relatively oxygen-reduced conditions. They also show a slight enrichment in alkali elements (Rb and Cs) and post-transition elements (Ga), and LREE, indicating intense weathering. The Ga/Rb and K/Al values further support warm and humid Cretaceous conditions. Thus, the Turonian-Coniacian strata offer valuable information about ancient environments, climate conditions, and the basin evolution of the Tethys Ocean in the Eastern Black Sea region.

Liquid state of post-transition metals for interfacial synthesis of two-dimensional materials

The nascent field of liquid metals, metals, and alloys of low melting points has provided opportunities for synthesizing low-dimensional materials. Located between transition- and non-metals in the periodic table, post-transition elements exhibit unique properties in particular low melting points. Taking on a liquid form at low temperature, post-transition liquid metals can be used as solvents for metallic solutes. The enigmatic surface of liquid metals is also ultra-active and smooth, offering opportunities for fabricating and templating two-dimensional (2D) films. So far, various 2D materials have been harvested from the surface of liquid metals including 2D metal compounds and nonmetallic materials. Utilizing different extraction and transfer techniques, the produced 2D films can be uniformly deposited on desired substrates at large lateral dimensions. Here, we present a comprehensive overview of the fundamentals underlying post-transition-elements-based liquid metals and alloys and explain the effect of atomic level electron configurations on their characteristics. We discuss the key physical properties of liquid metals including the origin of their low melting points and their high thermal and electrical conductivities. We illustrate their boundary-induced layering and oxidation as essential traits for creating 2D films. Afterward, the interfacial synthesis of 2D materials is depicted with the discussion of surface oxidation, reduction and exfoliation. We present different types of devices using liquid metal-induced 2D synthesis processes, including field-effect transistors, optoelectronic devices, systems that use 2D dielectric and conductive layers, and piezoelectric devices. Eventually, we discuss future prospects and outline how liquid metals can contribute to exciting future applications.

Stereoselective formation of bismuth complexes by transmetalation of lead with adaptable overhanging carboxylic acid 5,10-strapped porphyrins

Out-of-plane deformations of metalloporphyrin skeletons have been well documented as playing important roles in relevant biological processes. In contrast, out-of-plane binding to the N-core of large metal cations as period 6 post-transition elements has remained poorly investigated. We describe herein monometallic complexes of Pb(II) and Bi(III) with 5,10 single strapped porphyrin ligands bearing a carboxylic acid group with two possible “in/out” orientations, in which the metal ions are bound to the N-core of the macrocycle either from the strap side or from the naked side. In the case of Pb(II), both the kinetics of insertion and resulting OOP stereoselectivity are influenced by the “in/out” stereoisomerism of the overhanging COOH. Remarkably, Bi(III) insertion proceeded quasi-instantaneously at RT owing to the transmetalation of its Pb(II) counterpart. The addition of a cyano group in position of the carboxylic acid group generates a ligand exhibiting an increased stereoselectivity in the metalation processes with Pb(II) and Bi(III): these cations are coordinated exclusively from the naked and strap side of the macrocycle, respectively. This difference in behavior is likely explained by steric hindrance for the divalent cation, which is counterbalanced by the establishment of the second sphere of coordination with the strap for the trivalent cation. Such a behavior is thought of interest for the further design of adaptable supramolecular coordination assemblies.

Exploring the frontier between polar intermetallics and Zintl phases for the examples of the prolific ALnTnTe3-type alkali metal (A) lanthanide (Ln) late transition metal (Tn) tellurides

Abstract Understanding electronic structures is important in order to interpret and to design the chemical and physical properties of solid-state materials. Among those materials, tellurides have attracted an enormous interest, because several representatives of this family are at the cutting edge of basic research and technologies. Despite this relevance of tellurides with regard to the design of materials, the interpretations of their electronic structures have remained challenging to date. For instance, most recent research on tellurides, which primarily comprise post-transition elements, revealed a remarkable electronic state, while the distribution of the valence electrons in tellurides comprising group-I/II elements could be related to the structural features by applying the Zintl-Klemm-Busmann concept. In the cases of tellurides containing transition metals the applications of the aforementioned idea should be handled with care, as such tellurides typically show characteristics of polar intermetallics rather than Zintl phases. And yet, how may the electronic structure look like for a telluride that consists of a transition metal behaving like a p metal? To answer this question, we examined the electronic structure for the quaternary RbTbCdTe3 and provide a brief report on the crystal structures of the isostructural compounds RbErZnTe3 and RbTbCdTe3, whose crystal structures have been determined by means of X-ray diffraction experiments for the very first time.

Transition Metal Chain Complexes Supported by Soft Donor Assembling Ligands.

The chemistry of discrete molecular chains constituted by metals in low oxidation states, displaying metal-metal proximity and stabilized by suitable metal-bridging, assembling ligands comprising at least one soft donor atom is comprehensively reviewed; complexes with a single (hard or soft) bridging atom (e.g., μ-halide, μ-sulfide, or μ-PR2 etc.) as well as "closed" metal arrays (that fall in the realm of cluster chemistry) are excluded. The focus is on transition metal-based systems, with few excursions to cases combining transition and post-transition elements. Most relevant supporting ligands have neutral C, P, O, or S donor (mainly, N-heterocyclic carbene, phosphine, ether, thioether) or anionic donor (mainly phenyl, ylide, silyl, phosphide, thiolate) groups. A supporting-ligand-based classification of the metal chains is introduced, using as the classifying parameter the number of "bites" (i.e., ligand bridges) subtending each intermetallic separation. The ligands are further grouped according to the number of donor atoms interacting with the metal chain (called denticity in the following) and the column of the Periodic Table to which the set of donor atoms belongs (in ascending order). A complementary metal-based compilation of the complexes discussed is also provided in a concise tabular form.

Proton induced L-shell cross-sections for some post-transition metals: A comparison of ECPSSR and SCA models

The L-shell ionisation and X-ray production cross-sections of some post-transition elements: In, Sn and Tl, induced by protons of energies 1 MeV–4 MeV, have been calculated. The targets considered have few experimental cross-sections, for indium and tin, while thallium has no existing cross-section values in the database due to its radioactive and toxic nature. The cross-sections for the targets were obtained using computer codes based on the ECPSSR and SCA theories; and were subsequently validated using lead and bismuth targets whose experimental values are known within this energy range. The comparison of the experimental and calculated cross-sections showed that both models are in good agreement within certain proton energy region. However, above 2 MeV, the ECPSSR models should be employed. For the case where the SCA model is to be employed, the energy loss and Coulomb deflection factors should be taken into account.

Bond-length distributions for ions bonded to oxygen: metalloids and post-transition metals

Bond-length distributions have been examined for 33 configurations of the metalloid ions and 56 configurations of the post-transition metal ions bonded to oxygen, for 5279 coordination polyhedra and 21 761 bond distances for the metalloid ions, and 1821 coordination polyhedra and 10 723 bond distances for the post-transition metal ions. For the metalloid and post-transition elements with lone-pair electrons, the more common oxidation state between n versus n+2 is n for Sn, Te, Tl, Pb and Bi and n+2 for As and Sb. There is no correlation between bond-valence sum and coordination number for cations with stereoactive lone-pair electrons when including secondary bonds, and both intermediate states of lone-pair stereoactivity and inert lone pairs may occur for any coordination number > [4]. Variations in mean bond length are ∼0.06–0.09 Å for strongly bonded oxyanions of metalloid and post-transition metal ions, and ∼0.1–0.3 Å for ions showing lone-pair stereoactivity. Bond-length distortion is confirmed to be a leading cause of variation in mean bond lengths for ions with stereoactive lone-pair electrons. For strongly bonded cations (i.e. oxyanions), the causes of mean bond-length variation are unclear; the most plausible cause of mean bond-length variation for these ions is the effect of structure type, i.e. stress resulting from the inability of a structure to adopt its characteristic a priori bond lengths.

Liquid metals: fundamentals and applications in chemistry.

Post-transition elements, together with zinc-group metals and their alloys belong to an emerging class of materials with fascinating characteristics originating from their simultaneous metallic and liquid natures. These metals and alloys are characterised by having low melting points (i.e. between room temperature and 300 °C), making their liquid state accessible to practical applications in various fields of physical chemistry and synthesis. These materials can offer extraordinary capabilities in the synthesis of new materials, catalysis and can also enable novel applications including microfluidics, flexible electronics and drug delivery. However, surprisingly liquid metals have been somewhat neglected by the wider research community. In this review, we provide a comprehensive overview of the fundamentals underlying liquid metal research, including liquid metal synthesis, surface functionalisation and liquid metal enabled chemistry. Furthermore, we discuss phenomena that warrant further investigations in relevant fields and outline how liquid metals can contribute to exciting future applications.

Catalytic activity of corrole complexes with post-transition elements for the oxidation of carbon monoxide: a first-principles study

Our theoretical investigation shows that the aluminum and gallium complexes of corrole can be considered as potential high-performance catalysts for the oxidation of CO.

Layered Structures and Disordered Polyanionic Nets in the Cation-Poor Polar Intermetallics CsAu1.4Ga2.8 and CsAu2Ga2.6

Gold intermetallics are known for their unusual structures and bonding patterns. Two new compounds have been discovered in the cation-poor part of the Cs–Au–Ga system. Both compounds were obtained directly by heating the elements at elevated temperatures. Structure determinations based on single-crystal X-ray diffraction analyses revealed two structurally and compositionally related formations: CsAu1.4Ga2.8 (I) and CsAu2Ga2.6 (II) crystallize in their own structure types (I: R3, a = 11.160(2) A, c = 21.706(4) A, Z = 18; II: R3, a = 11.106(1) A, A, c = 77.243(9) A, Z = 54) and contain hexagonal cationic layers of cesium. This is a unique structural motif, which has never been observed for the other (lighter) alkali metals in combination with Au and post transition elements. The polyanionic part is characterized in contrast by Au/Ga tetrahedral stars, a structural feature that is characteristic for light alkali metal representatives, and disordered sites with mixed Au/Ga occupancies that occur in both str...

Electronic structure and local magnetism of 3d–5d impurity substituted CeFe2

We present here a systematic first-principles study of electronic structure and local magnetic properties of Ce[Fe0.75M0.25]2 compounds, where M is a 3d, 4d or 5d transition or post-transition element, using the generalized gradient approximation of the density functional theory. The d–f band hybridizations existing in CeFe2 get modified by the impurity M in an orderly manner across a period for each impurity series: the hybridization is strongest for the Mn group impurity in the period and gets diminished on either side of it. The weakening of the d–f hybridization strength is also associated with a relative localization of the Ce 4f states with respect to the delocalized 4f states in CeFe2. The above effects are most prominent for 3d impurity series, while for 4d and 5d impurities, the hybridizations and relocalizations are relatively weak due primarily to the relatively extended nature of 4d and 5d wavefunctions. The Ce local moment is found to decrease from the CeFe2 value in proportion to the strength of relocalization, thus following almost the same orderly trend as obeyed by the d–f hybridization. Further, depending on the way the spin-up and spin-down densities of states of an impurity shift relative to the Fermi energy, the impurity local moments are highest for Mn or Fe group, reduce on either side, become zero for Ni to Ga, and are small but negative for V and Ti. The Ce hyperfine field is found to follow the M local moment in a linear fashion, and vice–versa.

A Universal Wet-Chemistry Route to Metal Filling of Boron Nitride Nanotubes.

We present a facile wet-chemistry method for efficient metal filling of the hollow inner cores of boron nitride nanotubes (BNNTs). The fillers conform to the cross-section of the tube cavity and extend in length from a few nm to hundreds of nm. The methodology is robust and is demonstrated for noble metals (Au, Pt, Pd, and Ag), transition metals (Co), and post-transition elements (In). Transmission electron microscopy and related electron spectroscopy confirm the composition and morphology of the filler nanoparticles. Up to 60% of BNNTs of a given preparation batch have some degree of metal encapsulation, and individual tubes can have up to 10% of their core volume filled during initial loading. The growth, movement, and fusing of metal nanoparticles within the BNNTs are also examined.

Crystal structure and bonding in BaAu5Ga2 and AeAu4+xGa3-x (Ae = Ba and Eu): hexagonal diamond-type Au frameworks and remarkable cation/anion partitioning in the Ae-Au-Ga systems.

Five new polar intermetallic compounds in the Ae-Ga-Au system (Ae = Ba, Eu), BaAu(5)Ga(2) (I), BaAu(4.3)Ga(2.7) (II), Ba(1.0)Au(4.5)Ga(2.4 )(III), EuAu(4.8)Ga(2.2) (IV), and Eu(1.1)Au(4.4)Ga(2.2) (V), have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. I crystallizes in the orthorhombic crystal system with a large unit cell [Pearson symbol oP64; Pnma, Z = 8, a = 8.8350(5) Å, b = 7.1888(3)Å, c = 20.3880(7) Å], whereas all other compounds are hexagonal [hP24; P6̅2m, Z = 3, a = 8.54-8.77(1) Å, c = 7.19-7.24(1) Å]. Both structures contain mutually orthogonal layers of Au(6) hexagons in chair and boat conformations, resulting in a hexagonal diamond-like network. Ae atoms and additional (Au/Ga)(3) groups are formally encapsulated by (Au(6))(2) distorted hexagonal prisms formed of three edge-sharing hexagons in the boat conformation or, alternatively, lie between two Au(6) hexagons in the chair conformation. The (Au/Ga)(3) groups can be substituted by Ae atoms in some of the hexagonal structures with no change to the structural symmetry. Tight-binding electronic structure calculations using linear-muffin-tin-orbital methods on idealized models "BaAu(5)Ga(2)" and "BaAu(4)Ga(3)" show both compounds to be metallic with evident pseudogaps near the corresponding Fermi levels. The integrated crystal orbital Hamilton populations are dominated by Au-Au and Au-Ga orbital interactions, although Ba-Au and Ba-Ga contributions are significant. Furthermore, Au-Au interactions vary considerably along different directions in the unit cells, with the largest values for the hexagons in the boat conformation and the lowest values for those in the chair conformation. II revealed that partial substitution of Au atoms in the hexagonal diamond net by a post-transition element (Ga) may occur in this family, whereas the sizes of the (Au/Ga)(3) groups and strong Ba-Au covalent interactions allow for their mutual replacement in the voids.

Heavy metal boryl chemistry: complexes of cadmium, mercury and lead

Synthetic routes to the first boryl complexes of cadmium and mercury are reported via transmetallation from boryllithium; the syntheses of related group 14 systems highlight the additional factors associated with extension to more redox-active post-transition elements.

Endohedral Beryllium Atoms in Germanium Clusters with Eight and Fewer Vertices: How Small Can a Cluster Be and Still Encapsulate a Central Atom?

Structures of the beryllium-centered germanium clusters Be@Ge(n)(z) (n = 8, 7, 6; z = -4, -2, 0, +2) have been investigated by density functional theory to provide some insight regarding the smallest metal cluster that can encapsulate an interstitial atom. The lowest energy structures of the eight-vertex Be@Ge(8)(z) clusters (z = -4, -2, 0, +2) all have the Be atom at the center of a closed polyhedron, namely, a D(4d) square antiprism for Be@Ge(8)(4-), a D(2d) bisdisphenoid for Be@Ge(8)(2-), an ideal O(h) cube for Be@Ge(8), and a C(2v) distorted cube for Be@Ge(8)(2+). The Be-centered cubic structures predicted for Be@Ge(8) and Be@Ge(8)(2+) differ from the previously predicted lowest energy structures for the isoelectronic Ge(8)(2-) and Ge(8). This appears to be related to the larger internal volume of the cube relative to other closed eight-vertex polyhedra. The lowest energy structures for the smaller seven- and six-vertex clusters Be@Ge(n)(z) (n = 7, 6; z = -4, -2, 0, +2) no longer have the Be atom at the center of a closed Ge(n) polyhedron. Instead, either the Ge(n) polyhedron has opened up to provide a larger volume for the Be atom or the Be atom has migrated to the surface of the polyhedron. However, higher energy structures are found in which the Be atom is located at the center of a Ge(n) (n = 7, 6) polyhedron. Examples of such structures are a centered C(2v) capped trigonal prismatic structure for Be@Ge(7)(2-), a centered D(5h) pentagonal bipyramidal structure for Be@Ge(7), a centered D(3h) trigonal prismatic structure for Be@Ge(6)(4-), and a centered octahedral structure for Be@Ge(6). Cluster buildup reactions of the type Be@Ge(n)(z) + Ge(2) → Be@Ge(n+2)(z) (n = 6, 8; z = -4, -2, 0, +2) are all predicted to be highly exothermic. This suggests that interstitial clusters having an endohedral atom inside a bare post transition element polyhedron with eight or fewer vertices are less than the optimum size. This is consistent with the experimental observation of several types of 10-vertex polyhedral bare post transition element clusters with interstitial atoms but the failure to observe such clusters with external polyhedra having eight or fewer vertices.

The sphericity of the diverse 10-vertex polyhedra found in bare post-transition metal clusters: germanium clusters with interstitial magnesium atoms as model systems

The diverse polyhedra found experimentally in bare 10-vertex centered post-transition element clusters characterized structurally by X-ray crystallography include the D 4d bicapped square antiprism Zn@In 10 8− in the intermetallic K8In10Zn as well as the centered lead clusters M@Pb10 2− in [K(2,2,2-crypt)]2[M@Pb10] (M = Ni, Pd, Pt), the C3v tetracapped trigonal prism M@In 10 10− in the intermetallic K10In10M (M = Ni, Pd, Pt), the D 5d pentagonal antiprism Pd@Bi10 4+ in Bi14PdBr16, and the D 5h pentagonal prism in the trianions M@Ge 10 3− (M = Fe, Co). The structures of the 10-vertex germanium clusters containing an interstitial magnesium atom (atomic radius 1.30 A), namely Mg@Ge 10 (z = +2, 0, −2, −4), have been optimized as models to analyze the frontier molecular orbitals of the four experimentally known 10-vertex polyhedra noted above. In this connection, the molecular orbital patterns of the most spherical D 4d bicapped square antiprism cluster Mg@Ge10 as well as that of an approximately spherical C 3v cluster Mg@Ge 10 2+ derived from the tetracapped trigonal prism exhibit the spherical harmonic ordering of the jellium model. In this ordering scheme, the 20-orbital {1s, 1p, 1d, 2s, 1f, 2p} shell is filled before any of the 1g molecular orbitals. However, the molecular orbital patterns of the oblate D 5d pentagonal antiprism cluster Mg@Ge 10 4− and the D 5h pentagonal prism cluster Mg@Ge10 no longer exhibit the spherical harmonic ordering of the jellium model. In these clusters, the polar 1f(z 3) orbital is raised to antibonding levels and the pair of hexagonal prism g molecular orbitals become bonding orbitals. The sphericities of the four distinct 10-vertex polyhedra found experimentally in centered bare 10-vertex post-transition metal clusters have been evaluated by comparing the relative energies of the cluster bonding molecular orbitals in model Mg@Ge 10 (z = −4 to +2) species with the spherical harmonic ordering predicted by the jellium model. Using this as a criterion, the D 4d bicapped square antiprismatic and C 3v tetracapped trigonal prismatic structures can be regarded as essentially spherical. However, the molecular orbital patterns of the oblate D 5d pentagonal antiprismatic and D 5h pentagonal prismatic clusters deviate significantly from spherical harmonic ordering.

Four Polyanionic Compounds in the K–Au–Ga System: A Case Study in Exploratory Synthesis and of the Art of Structural Analysis

The K-Au-Ga system has been investigated at 350 °C for <50 at. % K. The potassium gold gallides K(0.55)Au(2)Ga(2), KAu(3)Ga(2), KAu(2)Ga(4) and the solid solution KAu(x)Ga(3-x) (x = 0-0.33) were synthesized directly from the elements via typical high-temperature reactions, and their crystal structures were determined by single crystal X-ray diffraction: K(0.55)Au(2)Ga(2) (I, I4/mcm, a = 8.860(3) Å, c = 4.834(2) Å, Z = 4), KAu(3)Ga(2) (II, Cmcm, a = 11.078(2) Å, b = 8.486(2) Å, c = 5.569(1) Å, Z = 4), KAu(2)Ga(4) (III, Immm, a = 4.4070(9) Å, b = 7.339(1) Å, c = 8.664(2) Å, Z = 2), KAu(0.33)Ga(2.67) (IV, I-4m2, a = 6.0900(9) Å, c = 15.450(3) Å, Z = 6). The first two compounds contain different kinds of tunnels built of puckered six- (II) or eight-membered (I) ordered Au/Ga rings with completely different cation placements: uniaxial in I and III but in novel 2D-zigzag chains in II. III contains only infinite chains of a potassium-centered 20-vertex polyhedron (K@Au(8)Ga(12)) built of ordered 6-8-6 planar Au/Ga rings. The main structural feature of IV is dodecahedral (Au/Ga)(8) clusters. Tight-binding electronic structure calculations by linear muffin-tin-orbital methods were performed for idealized models of I, II, and III to gain insights into their structure-bonding relationships. Density of states curves reveal metallic character for all compounds, and the overall crystal orbital Hamilton populations are dominated by polar covalent Au-Ga bonds. The relativistic effects of gold lead to formation of bonds of greater population with most post-transition elements or to itself, and these appear to be responsible for a variety of compounds, as in the K-Au-Ga system.

ChemInform Abstract: Homoatomic Polyanions of Post-Transition Elements. Synthesis, Structure, and Characterization of the Paramagnetic Nonagermanide (3-) Ion Ge3- 9, a C2v Cluster with an Odd Skeletal Electron Count.

The salt K3(2,2,2-cryptand)3(PPh3)3Ge9 has been obtained by complexation of the KGe1.8 alloy by 2,2,2-cryptand in ethylenediamine with solute triphenylphosphine. The structure of the anion has been determined crystallographically and the results are supported by EPR and extended Huckel calculations.

The role of “external” lone pairs in the chemical bonding of bare post-transition element clusters: the Wade–Mingos rules versus the jellium model

The jellium sphere model of a volume of electrons, counterbalanced by a positive charge throughout the sphere, leads to an energy level sequence corresponding to special stabilities of bare post-transition element clusters with 20 valence electrons such as the known P4 and clusters with 40 valence electrons such as the known Ge9(4-), Ni@In10(10-), and In11(7-). In this model the otherwise "external" lone pairs on the vertex atoms participate at least indirectly in the skeletal bonding. Furthermore, this model predicts the most favorable polyhedra and electron counts in some cases to be quite different than those predicted by the Wade-Mingos rules of polyhedral borane chemistry.

Stereochemistry of Pb(II) Complexes with Aminopolycarboxylic Ligands. The Role of a Lone Electron Pair

The structures of complex anions of Pb(II) coordination compounds (complexonates) with monoamino-, diamino-, and polyaminopolycarboxylic acids as ligands were interpreted in terms of a model of the valence shell electron pair repulsion. A lone electron pair (E) in all structurally studied Pb(II) complexonates with carboxyl-containing complexones was shown to be stereochemically active, and the structure of Pb coordination polyhedron was found to depend on both the ligand dentate number and on its degree of protonation. As the ligand dentate number increased, the coordination number (C.N.) of a central atom changed from 4 + E for monoamine complexonates to 6 + E for diamine and triamine complexonates. With allowance for secondary bonds in the structure, the C.N. of the Pb atom increased to 7–9. The Pb(II) complexonates with nitrilotriacetic acid exhibit the formation of a new type of coordination polyhedron for post-transition elements in a low-valent state with five electron pairs in a valence shell (including one lone electron pair), i.e., the ψ-trigonal bipyramid with E in the axial position.