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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

  • Katharina Eickmeier and Simon Steinberg EMAIL logo
Published/Copyright: September 20, 2021
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 76 Issue 10-12

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.

Keywords: bonding analyses; electronic structures; intermetallics; tellurides

1 Introduction

The lack [1, 2] of concepts to generally account for the chemical and physical features of solid state materials, especially intermetallics, typically poses a challenge regarding their tailored design. Therefore, quantum-chemical means are typically at play in the designs of solid-state materials, because the interpretation [3], [4], [5] of the electronic structure for a given solid state material facilitates to identify, to understand, and to forecast its chemical and physical features. One most recent example that underlines the need for such quantum-chemical efforts includes the introduction [6] of a new group of solid-state materials dubbed incipient metals. These materials were proposed [7], [8], [9] to show an electronic state that is solely encountered for the representatives of the aforementioned family. While this electronic state was expected to arise from competitions between valence electron localization and delocalization, additional research [10], [11], [12] allowed to relate the bonding nature of such materials to concepts well established in chemistry. While this research mainly focused on chalcogenides containing post-transition elements, one may wonder how the electronic structures of chalcogenides composed of alkali metals, alkaline earth and/or transition metal elements could be described.

In the cases of tellurides, which have been intensively investigated due to the remarkable properties [13], [14], [15], [16], [17], [18] of several representatives of this family, the relationships between the structural characteristics and the distribution of the valence electrons have been typically [19, 20] interpreted by applying the Zintl-Klemm-Busmann concept. This idea [21], [22], [23], [24], [25], [26] was originally developed to relate the structural features to the valence electron distributions in intermetallics, which are solely composed of main group elements, and it has been extended by diverse approaches. Within this idea, the valence electrons are expected to be transferred from the more electropositive to the more electronegative elements, which constitute fragments or clusters isostructural to the arrangements of the isoelectronic elements. Although, the predictions derived from applications of this concept apply well [7, 27] to tellurides containing alkali and alkaline earth elements, yet, things look different [28], [29], [30], [31], [32] for certain tellurides containing transition metal elements. The most recent research on tellurides containing transition metals showed that relationships between the structural features and the distributions of the valence electrons cannot be understood by application of the Zintl-Klemm-Busmann idea (despite certain trends that can be derived from these treatments). As these tellurides also contain certain polyionic fragments associated with monoatomic counterions, it was indicated that these tellurides should be assigned to the family of the polar intermetallics [33], [34], [35] rather than to that of the Zintl compounds. As these studies have focused on transition metals which contribute to the interatomic interactions via their d orbitals, one may wonder how things will look like for transition metals that can [36], [37], [38] also behave like a p-block element.

In this connection, most recent research [39] on a telluride containing zinc demonstrated that this telluride shows attributes of a polar intermetallic compound, although the relationship between the structural features and the electronic structure could also be understood by a Zintl-Klemm-Busmann treatment. To explore if this conclusion can also be drawn for a telluride containing cadmium, we followed up with an examination of the electronic structure of the quaternary compound RbTbCdTe3. In this contribution, we present the results of our explorations of the electronic structure of the latter telluride. Furthermore, we provide a brief overview for this type of tellurides along with a report of the crystal structures for the examples of the isostructural compounds RbErZnTe3 and RbTbCdTe3, which were obtained from solid-state syntheses for the first time.

2 Experimental section

2.1 Syntheses

RbErZnTe3 and RbTbCdTe3 were obtained from reactions of the respective rare earth elements, the corresponding transition metals, tellurium, and rubidium chloride. Because the rare earth elements [40] as well as the obtained products are sensitive against air and moisture, all sample preparations had to be accomplished within an argon-filled glove box (MBraun®, Garching, Germany; H2O, O2 < 0.1 ppm by volume). From the RbCl (99.8%; Sigma Aldrich®, St. Louis, MO, USA) that was employed as a reactive flux [41], traces of water were removed under a reduced atmosphere prior to its transfer into the aforementioned glove box. Powders of the rare earth elements (Tb: 99.95%; Er: 99.95%; smart-elements®, Vienna, Austria) were obtained by filing larger ingots, while the transition metals (Zn: 99.995%; powder; laborhandel.de, Hüfingen, Germany; Cd: 99.9999%; wire; Koch-Light Laboratories® Ltd., Coinbrook Bucks, UK) and tellurium (>99%; Merck®, Darmstadt, Germany) were utilized without further purification. The starting materials were weighed in the desired ratios, thoroughly homogenized and loaded into one-side closed silica tubes, which were closed in the glove box with the aid of quickfit adapters. The latter were connected to a Schlenk line outside the glove box in order to flame-seal the loaded silica tubes under a reduced atmosphere of at least 2 × 10−3 mbar. The reaction mixtures were heated using computer-controlled tube furnaces and the following temperature programs: RbErZnTe3: heat to 850 °C within 30 h, keep that temperature for 96 h, cool to 300 °C with a rate of 4 K h−1 and equilibrate to room temperature within 3 h; RbTbCdTe3: heat to 850 °C with a rate of 30 K h−1, hold at that temperature for four days, cool down to 200 °C with a rate of 3 K h−1, and, finally, to room temperature within 2 h. The products appeared as black powders with metallic luster and contained small single crystals which were used for further analyses (see below). Phase analyses based on powder X-ray diffraction patterns which were collected for the samples revealed that the quaternary tellurides were obtained in considerable yields, but that they were also accompanied by side products (Figure 1).

Figure 1: Measured (top) powder X-ray diffraction patterns of the samples containing the quaternary tellurides and simulated (bottom) powder X-ray diffraction patterns of (a) RbErZnTe3 and (b) RbTbCdTe3: reflections related to side-products Zn3TeO6 [42], ZnTe [43], and RbCl [44] are marked as indicated.
Figure 1:

Measured (top) powder X-ray diffraction patterns of the samples containing the quaternary tellurides and simulated (bottom) powder X-ray diffraction patterns of (a) RbErZnTe3 and (b) RbTbCdTe3: reflections related to side-products Zn3TeO6 [42], ZnTe [43], and RbCl [44] are marked as indicated.

2.2 X-ray diffraction experiments

To determine the yield of the quaternary tellurides and to detect any side-products, phase analyses were carried out based on powder X-ray diffraction patterns which were collected for the different samples. The powder X-ray diffraction patterns were compared to those patterns which were simulated for the quaternary tellurides as well as the expected side-products. Prior to the collections of the powder X-ray diffraction data, the samples were finely ground and loaded into capillaries that were subsequently sealed within the glove box. The powder X-ray diffraction experiments were carried out at room temperature using a STOE® StadiP diffractometer (CuKα radiation; λ = 1.54059 Å; STOE® & Cie GmbH; Darmstadt, Germany), while the WinXPow software package [45] was employed for controlling the aforementioned measurements and further processing of the raw data. The phase analyses, which were accomplished by comparing the powder X-ray diffraction patterns collected for the samples to those simulated for by-products, were carried out by means of the Match! [46] code.

To collect sets of single-crystal X-ray intensity data, samples were selected from the bulk materials and fixed in capillaries that were sealed within the glove box. The samples were transferred to a Bruker® APEX CCD diffractometer (Bruker® Inc.; Madison, WI, USA) that was employed for initial testing of the quality of the selected samples and for the collection of the sets of single-crystal X-ray intensity data at room temperature (MoKα radiation; λ = 0.71073 Å). The raw intensity data was integrated using the Saint code, while multi-scan absorption corrections were carried out using the program Sadabs [47]. The application of the reflection conditions to the single-crystal X-ray intensity data sets were accomplished by means of the Xprep code [48] and indicated the space group Cmcm (no. 63), which was also used for the initial structure solutions by utilizing Direct Methods (Shelxs). Full-matrix least-squares refinements on F 2 which also included atomic anisotropic displacement parameters were completed using the Shelxl [49, 50] code. Details regarding the structure solutions and refinements of the quaternary tellurides may be extracted from Table 1, while the atomic positions and the respective equivalent isotropic displacement parameters of RbErZnTe3 and RbTbCdTe3 are provided in Table 2.

Table 1:

Details of the single-crystal X-ray measurements and data collection of the quaternary compounds RbErZnTe3 and RbTbCdTe3.

Composition RbErZnTe3 RbTbCdTe3
Molecular weight, g mol−1 700.90 739.59
Crystal system Orthorhombic
Space group Cmcm (no. 63)
a, Å 4.362(1) 4.499(6)
b, Å 16.076(2) 16.12(2)
c, Å 11.549(2) 11.79(2)
Unit cell volume V, Å3 809.8(2) 854.6(19)
Z 4
Calculated density D cald, g cm−3 5.75 5.75
Absorption coefficient μ, mm−1 29.7 26.3
F(000), e 1164 1224
θ range data collection, deg 2.53–30.92 2.53–24.51
Limiting indices hkl −6 ≤ h ≤ 6 −5 ≤ h ≤ 4
−15 ≤ k ≤ 22 −9 ≤ k ≤ 18
−16 ≤ l ≤ 15 −13 ≤ l ≤ 11
Collected reflections 3120 894
Independent reflections 716 403
R int 0.032 0.083
Reflections with I > 2 σ(I) 686 305
Refinement method Full-matrix least-squares on F 2
Data/restraints/parameter 716/0/23 403/0/23
Final R1/wR2 [F 2 > 2 σ(F 2)] 0.024/0.058 0.059/0.128
Final R1/wR2 (all data) 0.026/0.059 0.084/0.138
Goodness-of-fit on F 2 1.189 1.063
Largest diff. peak/hole Δρ, e Å−3 2.38/−1.93 2.34/−2.32
Table 2:

Atomic position and equivalent atomic displacement parameters of the quaternary compounds RbErZnTe3 and RbTbCdTe3.

Atom Wyckoff position X Y Z U eq (Å2)
RbErZnTe3
Er 4a 0 0 0 0.0129(1)
Te1 8f 0 0.3734(1) 0.0571(1) 0.0136(1)
Te2 4c 0 0.0641(1) 1/4 0.0119(1)
Rb 4c 0 0.7472(1) 1/4 0.0277(2)
Zn 4c 0 0.4610(1) 1/4 0.0165(2)
RbTbCdTe3
Tb 4a 0 0 0 0.0189(7)
Te1 8f 0 0.3704(2) 0.0489(2) 0.0201(6)
Te2 4c 0 0.0703(2) 1/4 0.0192(8)
Rb 4c 0 0.7501(3) 1/4 0.0339(14)
Cd 4c 0 0.4615(2) 1/4 0.0229(9)

Further details of the crystal structure investigations may be obtained from the joint CCDC/FIZ Karlsruhe online deposition service: https://www.ccdc.cam.ac.uk/structures/? by quoting the deposition number CSD-2097008 and CSD-2097045.

2.3 Computational details

To gain an insight into the bonding nature of the cadmium-containing telluride, chemical bonding analyses were carried out using first-principles-based methods. All electronic band structure computations, which also included full structural optimizations of the lattice parameters and atomic positions, were accomplished in a non-magnetic regime using the projector augmented wave [51] method (PAW) as implemented in the Vienna Ab-initio Simulation Package (VASP) [52], [53], [54], [55], [56]. Correlation and exchange in all computations that were carried out in a non-magnetic regime were described by the generalized gradient approximation of Perdew, Burke und Ernzerhof [57] (GGA-PBE), while the energy cut-off of the plane wave basis sets was 500 eV. A 24 × 6 × 8 k-points set was used to sample the first Brillouin zone, and all computations were considered to be converged as the energy difference between two iterative steps fell below 10−8 eV per cell (and 10−6 eV per cell) of the electronic (and ionic) relaxation.

The bonding analysis was accomplished based on the Mulliken and Löwdin charges [27] as well as the projected crystal orbital Hamilton populations [58] (pCOHP). The latter approach has been developed based on the COHP [59, 60] technique, for which the off-site entries of the density-of-states matrix are weighted with the respective Hamilton matrix elements. In doing so, it is possible to identify bonding, non-bonding, and antibonding interactions; however, the construction of the crystal orbitals requires the use of local basis sets, whose nature is in stark contrast to the delocalized one of the plane waves. Therefore, the results of the plane-wave-based computations had to be transferred into local representations involving all-electron contracted Slater-type orbitals. These projections were achieved with the aid of transfer matrices, which were applied to the results of the plane-wave-based computations by using the Local-Orbital Basis Suite Towards Electronic-Structure Reconstruction (Lobster) [58, 59, 61, 62] code. Within the framework of this process it is also possible to determine the gross populations which are subtracted from the respective valence electron counts to obtain the Mulliken and Löwdin charges. The Mulliken and Löwdin charges have been included in the representation showing the crystal structure of the quaternary tellurides (Figure 2), while representations of the DOS and –pCOHP, which were visualized with the aid of the wxDragon code [63], are shown in Figure 3.

Figure 2: Representation of the crystal structure of an ALnTnTe3-type telluride (here: RbTbCdTe3): the diverse types of tellurium polyhedra surrounding the rubidium, terbium, and cadmium atoms are shown in the respective insets, the corresponding averaged Mulliken and Löwdin charges (in parentheses) have also been included (all charges in units of the elementary charge e).
Figure 2:

Representation of the crystal structure of an ALnTnTe3-type telluride (here: RbTbCdTe3): the diverse types of tellurium polyhedra surrounding the rubidium, terbium, and cadmium atoms are shown in the respective insets, the corresponding averaged Mulliken and Löwdin charges (in parentheses) have also been included (all charges in units of the elementary charge e).

Figure 3: (a)–(b) Total as well as atom- and orbital-projected density-of-states (DOS) curves of the quaternary compound RbTbCdTe3: the orbital-projected DOS correspond to those states providing the largest contributions to the DOS in the energy regions near the Fermi level. The lower and upper horizontal lines represent the valence band maximum (VBM) and conduction band minimum (CBM), respectively. (d) Projected crystal orbital Hamilton population (pCOHP) curves of diverse interactions in RbTbCdTe3: the cumulative –IpCOHP per cell values and their percentages to the net bonding capacities have been included using the font color of the respective interactions.
Figure 3:

(a)–(b) Total as well as atom- and orbital-projected density-of-states (DOS) curves of the quaternary compound RbTbCdTe3: the orbital-projected DOS correspond to those states providing the largest contributions to the DOS in the energy regions near the Fermi level. The lower and upper horizontal lines represent the valence band maximum (VBM) and conduction band minimum (CBM), respectively. (d) Projected crystal orbital Hamilton population (pCOHP) curves of diverse interactions in RbTbCdTe3: the cumulative –IpCOHP per cell values and their percentages to the net bonding capacities have been included using the font color of the respective interactions.

3 Results and discussion

The quaternary compounds RbErZnTe3 and RbTbCdTe3 were obtained from reactions of the respective lanthanides, the corresponding transition metals, tellurium and the reactive flux rubidium chloride (see Experimental Details). Structure determinations based on X-ray diffraction experiments revealed that both tellurides crystallize with the KZrCuS3-type structure [64] which belongs to the prolific AM′M″Q3 family [65] (A = s-block element; M′ = d- or f-block element; Mʺ = d-block element; Q = chalcogen) that includes seven different [66] structure types. Previous research has mainly focused on the ALnTnTe3 series (A = Cs, Ln = rare earth elements; Tn = Zn, Cd), while our most recent explorative efforts have been dedicated to the less investigated rubidium-containing analogues (an overview of the hitherto reported ALnTnTe3-type compounds and their respective unit cell volumes may be extracted from Table 3). A comparison of the unit cell volumes of RbErZnTe3 and RbTbCdTe3 to those of the isostructural cesium-containing compounds shows that the unit cell volumes of the former tellurides are smaller than those of the latter because of the increased covalent radius [67] from rubidium (2.20 Å) to cesium (2.44 Å). Before we continue with an examination of the electronic structure of the cadmium-containing compound (in order to explore the frontier between Zintl phases and polar intermetallics), we provide a brief description of the crystal structure of this type of quaternary tellurides.

Table 3:

Overview about the hitherto reported ALnTnTe3 compounds (A = Rb, Cs; Ln = rare earth element; Tn = Zn, Cd) and their respective unit cell volumes: the literature referring to the original structure reports has been included; bold font represents compounds, whose crystal structures have been reported in this contribution for the first time.

Zn volume (Å3) Cd volume (Å3)
Y
CsYZnTe3 [68] 851.1(1)
La
CsLaZnTe3 [68] 911.2(1) CsLaCdTe3 [69] 942.8(6)
Pr
CsPrZnTe3 [68] 891.6(2) CsPrCdTe3 [69] 926.2(11)
Nd
CsNdZnTe3 [68] 883.9(2) CsNdCdTe3 [69] 916.7(1)
Sm
CsSmZnTe3 [68] 871.4(2) CsSmCdTe3 [69] 908.9(2)
Gd RbGdZnTe3 [39] 832.0(4)
CsGdZnTe3 [68] 863.6(1) CsGdCdTe3 [69] 894.9(6)
Tb RbTbZnTe3 [39] 822.3(4) RbTbCdTe 3 854.6(19)
CsTbZnTe3 [68] 857.1(1) CsTbCdTe3 [69] 888.6(1)
Dy RbDyZnTe3 [39] 831.0(5)
CsDyZnTe3 [68] 851.1(1) CsDyCdTe3 [69] 882(2)
Ho
CsHoZnTe3 [68] 847.5(5) CsHoCdTe3 [69] 881.3(5)
Er RbErZnTe 3 809.8(2)
CsErZnTe3 [68] 840.2(3) CsErCdTe3 [69] 878.2(5)
Tm
CsTmZnTe3 [68] 836.6(2) CsTmCdTe3 [69] 877.1(7)
Yb RbYbZnTe3 [70] 792.5(2)
CsYbZnTe3 [70] 833.9(2)
Lu
CsLuCdTe3 [69] 873.6(15)

The crystal structure of this type of quaternary tellurides is composed of different types of tellurium polyhedra enclosing the alkali metal, the transition metal, and the lanthanide atoms. The transition metal atoms reside in the centers of tellurium tetrahedra, which are condensed via common vertices into linear chains, [Tn @ Te4] along the a axis, while the lanthanide atoms are surrounded by the tellurium atoms in an octahedral fashion. These [Ln @ Te6] octahedra are connected to two neighboring [Ln @ Te6] octahedra via common edges within 1[Ln @ Te6] chains, which share common vertices with nearest neighboring 1[Ln @ Te6] chains being tilted relative to each other. The [Tn @ Te4] chains are located in the voids between the 1[Ln @ Te6] chains such that these sorts of chains constitute puckered sheets parallel to the ac plane. Such sheets sandwich the alkali metal atoms occupying the centers of bicapped trigonal prisms made up of tellurium atoms. These [A @ Te8] units are condensed via the trigonal bases of the prisms into linear chains, [A @ Te8] propagating parallel to the a axis.

In the cases of Zintl phases, it should be possible to relate these structural features to the distributions of the valence electrons by applying the Zintl-Klemm-Busmann concept, while such crystal structure–electronic structure relationships are not evident for polar intermetallics [35]. As indicated by formula (A+)(Ln3+)(Tn2+)(Te2−)3, an application of the aforementioned idea to the quaternary tellurides points to an electron-precise distribution of the valence electrons. Furthermore, the analysis of the crystal structure for this type of telluride did not reveal any structural features which cannot be related to the distributions of the valence electrons by means of a Zintl-Klemm-Busmann treatment. Therefore, one may infer that this type of telluride could be regarded as a Zintl phase; yet, the Mulliken and Löwdin charges of RbTbCdTe3 (Figure 2) are indicative of an electronic structure being different from the predictions of the Zintl-Klemm-Busmann treatment.

A Mulliken and Löwdin population analysis of RbTbCdTe3 reveals that the charges of the rubidium atoms are close to the Zintl-Klemm-Busmann ideal, while the charges of the terbium, cadmium and tellurium atoms are evidently smaller than those charges predicted by the application of the aforementioned concept. Because there is a nearly complete valence electron transfer from the rubidium to the tellurium atoms, it may be concluded that closed-shell species with polar attractive forces are evident for the rubidium–tellurium bonds, which, accordingly, should be classified as ionic. This conclusion is also corroborated from an analysis of the density-of-states (DOS) for the quaternary telluride: as the rubidium 5s states are located above the conduction band minimum (not shown in Figure 3), it may be inferred that the rubidium atoms are oxidized and act as one-electron donors. Because the Mulliken and Löwdin charges of the terbium, cadmium, and tellurium atoms differ from the Zintl-Klemm-Busmann ideal, it is clear that these bonds cannot be described as ionic.

An inspection of the DOS curves (Figure 3) for RbTbCdTe3 also reveals that the Fermi level of this quaternary telluride falls in a broad band gap – a circumstance that typically [71], [72], [73] points to an electronically favorable situation for a given solid-state material. Furthermore, one may also expect that such characteristics at the Fermi level suggest to place this quaternary telluride in the family of the Zintl phases, as the Fermi levels of Zintl phases are often [74] located within band gaps. On the other hand, previous research [33] on the Fermi level characteristics of certain polar intermetallics showed that the Fermi levels of such materials may also be located within band gaps. A closer examination of the DOS in the energy regions near the Fermi level shows that the states close to the valence band maximum largely arise from the Te-5p and Cd-5s/4d atomic orbitals with minor contributions from the Tb-5d atomic orbitals. Accordingly, it could be concluded that these atomic orbitals overlap to form the Tb–Te and Cd–Te bonds, whose nature must be different from that of the Rb–Te bonds. To determine the nature of the former bonds, we carried out an analysis of the projected crystal orbital Hamilton population curves (pCOHP; Figure 3).

In the bonding analysis we focused on those atomic orbitals which provide the largest contributions to the states near the valence band maximum and, hence, are expected to overlap to form the heteroatomic bonds (see above). For the benefit of a better comparison, we also determined the percentages of the diverse bonds to the net bonding capabilities. To do so, the cumulative –IpCOHP per cell values, i.e. the sums of all –IpCOHP per bond values of a given sort of interatomic interaction within a unit cell, were projected as percentage contributions to the net bonding capacities – a procedure that been described in detail [60] elsewhere.

Although the Rb–Te bonds correspond to the largest number of contacts per unit cell (32), yet, these heteroatomic contacts have the smallest percentages to the net bonding capabilities. This is because the Rb-5s–Te-5p combinations are related to relatively small –IpCOHP per bond values (<–IpCOHP per bond> = 0.100 eV) as typically [60] encountered for bonds with a rather ionic character. Because the Tb-5d–Te-5p (<–IpCOHP per bond> = 1.085 eV) and Cd-5s/4d–Te-5p (<–IpCOHP per bond> = 0.709 eV) interactions correspond to higher –IpCOHP per bond values than the Rb–Te separations, it should be concluded that the former interactions show a much more bonding character relative to the latter bonds. This means that the valence electrons must be located between the terbium and tellurium atoms as well as between the cadmium and tellurium atoms like in a covalent bond. The presence of a covalent bonding contribution for the Tb–Te and the Cd–Te contacts is also backed by the results of the Mulliken and Löwdin population analysis, which clearly suggests open-shell species for the terbium, cadmium, and tellurium atoms. Accordingly, the modest valence electron transfer from the cadmium and terbium atoms to the tellurium atoms (as indicated by the Mulliken and Löwdin population analysis) and the locations of the valence electrons between the aforementioned atoms (as demonstrated by the –pCOHP bonding analysis) suggest that the Tb–Te and Cd–Te bonds should be categorized as polar covalent. Therefore, it could also be concluded that the quaternary telluride is composed of polar covalently bonded layers consisting of the terbium, cadmium, and tellurium atoms, while the rubidium atoms act as one-electron donors reducing the aforementioned layers – a picture that has also been previously [33] encountered for polar intermetallic phases.

4 Conclusions

Understanding the electronic structures in solid-state materials is decisive to explain and predict their chemical and physical properties. Valence electron (counting) rules, like the Zintl-Klemm-Busmann formalism, are useful tools to straightforwardly relate the structural features to the distributions of the valence electrons in a given solid-state material. To probe the limits of the aforementioned concept, we have now presented an analysis of the electronic structure of a quaternary telluride, i.e. RbTbCdTe3, which has been synthesized for the first time.

The analysis of the general structural features of this prolific kind of quaternary tellurides indicates that the structural characteristics of these tellurides can formally be related to the distributions of the valence electrons by means of a Zintl-Klemm-Busmann treatment. On the other hand, the results of the electronic structure computations for RbTbCdTe3 show that this sort of telluride is rather composed of polar covalently bonded layers consisting of the terbium, cadmium, and tellurium atoms, while the rubidium atoms act as one-electron donors, which are sandwiched between the aforementioned layers. The latter picture has also been encountered for polar intermetallic compounds, which, in contrast to the quaternary telluride, contain structural fragments that cannot be explained by means of a Zintl-Klemm-Busmann treatment. Therefore, it appears that this type of telluride is located at the frontier between polar intermetallic and Zintl phases.

Dedicated to: Professor Richard Dronskowski of the RWTH Aachen on the occasion of his 60th birthday.

Corresponding author: Simon Steinberg, Institute of Inorganic Chemistry, RWTH Aachen, Landoltweg 1, D-52074 Aachen, Germany, E-mail:

Funding source: Verband der Chemischen Industrie e.V. (FCI)

Acknowledgments

The authors wish to thank Prof. Richard Dronskowski for fruitful advice, providing laboratory space and the allocation of the computer cluster of the Chemistry Department of RWTH Aachen University. Furthermore, we wish to express thanks to Tobias Storp and Dr. Andreas Houben for the collections of the sets of single-crystal and powder X-ray diffraction data, respectively.

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This work was also supported by the Verband der Chemischen Industrie e.V. (FCI), Frankfurt a.M., through a Liebig stipend to S. S.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2021-07-27
Accepted: 2021-08-08
Published Online: 2021-09-20
Published in Print: 2021-11-25

© 2021 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Laudatio/Preface
  4. Celebrating the 60th birthday of Richard Dronskowski
  5. Review
  6. Orbital-selective electronic excitation in phase-change memory materials: a brief review
  7. Research Articles
  8. Solving the puzzle of the dielectric nature of tantalum oxynitride perovskites
  9. d- and s-orbital populations in the d block: unbound atoms in physical vacuum versus chemical elements in condensed matter. A Dronskowski-population analysis
  10. Single-crystal structures of A 2SiF6 (A = Tl, Rb, Cs), a better structure model for Tl3[SiF6]F, and its novel tetragonal polymorph
  11. Na2La4(NH2)14·NH3, a lanthanum-rich intermediate in the ammonothermal synthesis of LaN and the effect of ammonia loss on the crystal structure
  12. Linarite from Cap Garonne
  13. Salts of octabismuth(2+) polycations crystallized from Lewis-acidic ionic liquids
  14. High-temperature diffraction experiments and phase diagram of ZrO2 and ZrSiO4
  15. Thermal conversion of the hydrous aluminosilicate LiAlSiO3(OH)2 into γ-eucryptite
  16. Crystal structure of mechanochemically prepared Ag2FeGeS4
  17. Effect of nanostructured Al2O3 on poly(ethylene oxide)-based solid polymer electrolytes
  18. Sr7N2Sn3: a layered antiperovskite-type nitride stannide containing zigzag chains of Sn4 polyanions
  19. 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
  20. Zwitterion coordination to configurationally flexible d 10 cations: synthesis and characterization of tetrakis(betaine) complexes of divalent Zn, Cd, and Hg
  21. An approach towards the synthesis of lithium and beryllium diphenylphosphinites
  22. Synthesis, crystal and electronic structure of CaNi2Al8
  23. Crystal and electronic structure of the new ternary phosphide Ho5Pd19P12
  24. Synthesis, structure, and magnetic properties of the quaternary oxysulfides Ln 5V3O7S6 (Ln = La, Ce)
  25. Synthesis, crystal and electronic structure of BaLi2Cd2Ge2
  26. Structural variations of trinitrato(terpyridine)lanthanoid complexes
  27. Preparation of CoGe2-type NiSn2 at 10 GPa
  28. Controlled exposure of CuO thin films through corrosion-protecting, ALD-deposited TiO2 overlayers
  29. Experimental and computational investigations of TiIrB: a new ternary boride with Ti1+x Rh2−x+y Ir3−y B3-type structure
  30. Synthesis and crystal structure of the lanthanum cyanurate complex La[H2N3C3O3]3 · 8.5 H2O
  31. Cd additive effect on self-flux growth of Cs-intercalated NbS2 superconducting single crystals
  32. 14N, 13C, and 119Sn solid-state NMR characterization of tin(II) carbodiimide Sn(NCN)
  33. Superexchange interactions in AgMF4 (M = Co, Ni, Cu) polymorphs
  34. Copper(I) iodide-based organic–inorganic hybrid compounds as phosphor materials
  35. On iodido bismuthates, bismuth complexes and polyiodides with bismuth in the system BiI3/18-crown-6/I2
  36. Synthesis, crystal structure and selected properties of K2[Ni(dien)2]{[Ni(dien)]2Ta6O19}·11 H2O
  37. First low-spin carbodiimide, Fe2(NCN)3, predicted from first-principles investigations
  38. A novel ternary bismuthide, NaMgBi: crystal and electronic structure and electrical properties
  39. Magnetic properties of 1D spin systems with compositional disorder of three-spin structural units
  40. Amine-based synthesis of Fe3C nanomaterials: mechanism and impact of synthetic conditions
  41. Enhanced phosphorescence of Pd(II) and Pt(II) complexes adsorbed onto Laponite for optical sensing of triplet molecular dioxygen in water
  42. Theoretical investigations of hydrogen absorption in the A15 intermetallics Ti3Sb and Ti3Ir
  43. Assembly of cobalt-p-sulfonatothiacalix[4]arene frameworks with phosphate, phosphite and phenylphosphonate ligands
  44. Chiral bis(pyrazolyl)methane copper(I) complexes and their application in nitrene transfer reactions
  45. UoC-6: a first MOF based on a perfluorinated trimesate ligand
  46. PbCN2 – an elucidation of its modifications and morphologies
  47. Flux synthesis, crystal structure and electronic properties of the layered rare earth metal boride silicide Er3Si5–x B. An example of a boron/silicon-ordered structure derived from the AlB2 structure type
https://doi.org/10.1515/znb-2021-0100
Keywords for this article
bonding analyses; electronic structures; intermetallics; tellurides

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Laudatio/Preface
  4. Celebrating the 60th birthday of Richard Dronskowski
  5. Review
  6. Orbital-selective electronic excitation in phase-change memory materials: a brief review
  7. Research Articles
  8. Solving the puzzle of the dielectric nature of tantalum oxynitride perovskites
  9. d- and s-orbital populations in the d block: unbound atoms in physical vacuum versus chemical elements in condensed matter. A Dronskowski-population analysis
  10. Single-crystal structures of A 2SiF6 (A = Tl, Rb, Cs), a better structure model for Tl3[SiF6]F, and its novel tetragonal polymorph
  11. Na2La4(NH2)14·NH3, a lanthanum-rich intermediate in the ammonothermal synthesis of LaN and the effect of ammonia loss on the crystal structure
  12. Linarite from Cap Garonne
  13. Salts of octabismuth(2+) polycations crystallized from Lewis-acidic ionic liquids
  14. High-temperature diffraction experiments and phase diagram of ZrO2 and ZrSiO4
  15. Thermal conversion of the hydrous aluminosilicate LiAlSiO3(OH)2 into γ-eucryptite
  16. Crystal structure of mechanochemically prepared Ag2FeGeS4
  17. Effect of nanostructured Al2O3 on poly(ethylene oxide)-based solid polymer electrolytes
  18. Sr7N2Sn3: a layered antiperovskite-type nitride stannide containing zigzag chains of Sn4 polyanions
  19. 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
  20. Zwitterion coordination to configurationally flexible d 10 cations: synthesis and characterization of tetrakis(betaine) complexes of divalent Zn, Cd, and Hg
  21. An approach towards the synthesis of lithium and beryllium diphenylphosphinites
  22. Synthesis, crystal and electronic structure of CaNi2Al8
  23. Crystal and electronic structure of the new ternary phosphide Ho5Pd19P12
  24. Synthesis, structure, and magnetic properties of the quaternary oxysulfides Ln 5V3O7S6 (Ln = La, Ce)
  25. Synthesis, crystal and electronic structure of BaLi2Cd2Ge2
  26. Structural variations of trinitrato(terpyridine)lanthanoid complexes
  27. Preparation of CoGe2-type NiSn2 at 10 GPa
  28. Controlled exposure of CuO thin films through corrosion-protecting, ALD-deposited TiO2 overlayers
  29. Experimental and computational investigations of TiIrB: a new ternary boride with Ti1+x Rh2−x+y Ir3−y B3-type structure
  30. Synthesis and crystal structure of the lanthanum cyanurate complex La[H2N3C3O3]3 · 8.5 H2O
  31. Cd additive effect on self-flux growth of Cs-intercalated NbS2 superconducting single crystals
  32. 14N, 13C, and 119Sn solid-state NMR characterization of tin(II) carbodiimide Sn(NCN)
  33. Superexchange interactions in AgMF4 (M = Co, Ni, Cu) polymorphs
  34. Copper(I) iodide-based organic–inorganic hybrid compounds as phosphor materials
  35. On iodido bismuthates, bismuth complexes and polyiodides with bismuth in the system BiI3/18-crown-6/I2
  36. Synthesis, crystal structure and selected properties of K2[Ni(dien)2]{[Ni(dien)]2Ta6O19}·11 H2O
  37. First low-spin carbodiimide, Fe2(NCN)3, predicted from first-principles investigations
  38. A novel ternary bismuthide, NaMgBi: crystal and electronic structure and electrical properties
  39. Magnetic properties of 1D spin systems with compositional disorder of three-spin structural units
  40. Amine-based synthesis of Fe3C nanomaterials: mechanism and impact of synthetic conditions
  41. Enhanced phosphorescence of Pd(II) and Pt(II) complexes adsorbed onto Laponite for optical sensing of triplet molecular dioxygen in water
  42. Theoretical investigations of hydrogen absorption in the A15 intermetallics Ti3Sb and Ti3Ir
  43. Assembly of cobalt-p-sulfonatothiacalix[4]arene frameworks with phosphate, phosphite and phenylphosphonate ligands
  44. Chiral bis(pyrazolyl)methane copper(I) complexes and their application in nitrene transfer reactions
  45. UoC-6: a first MOF based on a perfluorinated trimesate ligand
  46. PbCN2 – an elucidation of its modifications and morphologies
  47. Flux synthesis, crystal structure and electronic properties of the layered rare earth metal boride silicide Er3Si5–x B. An example of a boron/silicon-ordered structure derived from the AlB2 structure type
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