Na3Ge2P3: A Zintl Phase Featuring [P3Ge-GeP3] Dimers as Building Blocks.

Recently, ternary lithium phosphidotetrelates have attracted interest particularly due to their high ionic conductivities, while corresponding sodium and heavier alkali metal compounds have been less investigated. Hence, we report the synthesis and characterization of the novel ternary sodium phosphidogermanate Na3Ge2P3, which is readily accessible via ball milling of the elements and subsequent annealing. According to single crystal X-ray structure determination, Na3Ge2P3 crystallizes in the monoclinic space group P21/c (no. 14.) with unit cell parameters of a = 7.2894(6) Å, b = 14.7725(8) Å, c = 7.0528(6) Å, ß = 106.331(6)° and forms an unprecedented two-dimensional polyanionic network in the b/c plane of interconnected [P3Ge-GeP3] building units. The system can also be interpreted as differently sized ring structures that interconnect and form a two-dimensional network. A comparison with related ternary compounds from the corresponding phase system as well as with the binary compound GeP shows that the polyanionic network of Na3Ge2P3 resembles an intermediate step between highly condensed cages and discrete polyanions, which highlights the structural variety of phosphidogermanates. The structure is confirmed by 23Na- and 31P-MAS NMR measurements and Raman spectroscopy. Computational investigation of the electronic structure reveals that Na3Ge2P3 is an indirect band gap semiconductor with a band gap of 2.9 eV.

All-Hydrocarbon-Ligated Superatomic Gold/Aluminum Clusters.

Key strategies in cluster synthesis include the use of modulating agents (e.g., coordinating additives). We studied the influence of various phosphines exhibiting different steric and electronic properties on the reduction of the Au(I) precursor to Au(0) clusters. We report a synthesis of the bimetallic clusters [Au6(AlCp*)6] = [Au6Al6](Cp*)6 (1) and [HAu7(AlCp*)6] = [HAu7Al6](Cp*)6 (2) (Cp* = pentamethylcyclopentadiene) using Au(I) precursors and AlCp*. The cluster [Au2(AlCp*)5] = [Au2Al5](Cp*)5 (3) was isolated and identified as an intermediate species in the reactions to 1 and 2. The processes of cluster growth and degradation were investigated by in situ 1H NMR and LIFDI-MS techniques. The structures of 1 and 2 were established by DFT geometry optimization. These octahedral clusters can both be described as closed-shell 18-electron superatoms.

Direct Band Gap Semiconductors with Two- and Three-Dimensional Triel-Phosphide Frameworks (Triel=Al, Ga, In).

Recently, several ternary phosphidotrielates and -tetrelates have been investigated with respect to their very good ionic conductivity, while less focus was pointed towards their electronic structures. Here, we report on a novel series of compounds, in which several members possess direct band gaps. We investigated the known compounds Li3AlP2, Li3GaP2, Li3InP2, and Na3InP2 and describe the synthesis and the crystal structure of novel Na3In2P3. For all mentioned phosphidotrielates reflectance UV-Vis measurements reveal direct band gaps in the visible light region with decreasing band gaps in the series: Li3AlP2 (2.45 eV), Li3GaP2 (2.18 eV), Li3InP2 (1.99 eV), Na3InP2 (1.37 eV), and Na3In2P3 (1.27 eV). All direct band gaps are confirmed by quantum chemical calculations. The unexpected property occurs despite different structure types. As a common feature all compounds contain EP4 tetrahedra, which share exclusively vertices for E=In and vertices as well as edges for E=Al and Ga. The structure of the novel Na3In2P3 is built up by a polyanionic framework of six-membered rings of corner-sharing InP4 tetrahedra. As a result, the newly designed semiconductors with direct band gaps are suitable for optoelectronic applications, and they can provide significant guidance for the design of new functional semiconductors.

Crystal structure of Ag3Dy2(NO3)9 and qu-anti-tative comparison to isotypic compounds.

Single crystals of Ag3Dy2(NO3)9 (tris-ilver didysprosium nona-nitrate) were obtained from a mixture of AgNO3 and Dy(NO3)3·5 H2O. The new compound crystallizes in space group P4132 (No. 213) with a = 13.2004 (4) Å, V = 2300.2 (2) Å3, Z = 4. The Ag and Dy cations are coordinated by five and six bidentate nitrate anions, respectively. Ag3Dy2(NO3)9 is isostructural to several compounds that include alkali metals or ammonium and lanthanide cations, but silver and dysprosium are included for the first time and feature the smallest ion radii observed for this structure type to date. Crystal structures of isotypic compounds are compared.

Crystal structure of sodium thio-sulfate dihydrate and comparison to the penta-hydrate.

Na2S2O3·2H2O has been mentioned in the literature for more than a hundred years and pure samples were prepared and investigated, however, no structural data except for a set of lattice parameters were known to date. Now crystals of this compound have been grown at the surface of an aqueous solution of Na2S2O3 and the structure has been determined at 200 and 100 K. Na2S2O3·2H2O crystallizes in the space group P21/n with two formula units in the asymmetric unit and all atoms occupying general positions. The sodium cations are five- to seven-coordinate by thio-sulfate anions and water mol-ecules and the anions act as mono- and bidentate ligands. In the extended structure, the thio-sulfate anions and water mol-ecules are connected by O-H⋯O and O-H⋯S hydrogen bonds of medium strength to form corrugated layers, which are linked by sodium cations. For comparison, the crystal structure of Na2S2O3·5H2O has been determined at the same conditions, i.e. for the first time below room temperature.

Oxidative coupling of silylated nonagermanide clusters.

Polyhedral main group element clusters of tetrel elements are discussed as suitable building units to form atom-precise nano-structures. Herein we report the oxidative coupling of two [Ge9{Si(TMS)3}2]2- clusters (TMS = trimethylsilyl) resulting in the dimeric cluster [Ge9{Si(TMS)3}2]22-. The dimer is structurally characterized as the [NHCiPrCu]+ adduct {NHCiPrCu[Ge9{Si(TMS)3}2]}2 [NHCiPr = 1,3-di(isopropyl)imidazolylidine]. The linkage of two molecular [Ge9{Si(TMS)3}2]2- anions under formation of an exo Ge-Ge bond occurs in the presence of Cy2BCl (Cy = cyclohexyl) and is mediated by trace amounts of oxygen as indicated by the isolation of the by-product Cy2B-O-BCy2.

Filled trivacant icosahedra as building fragments in 17-atom endohedral germanides [TM2@Ge17]n- (TM = Co, Ni).

The syntheses and the characterization of two 17-atom endohedral Ge clusters, [Co2@Ge17]6- (1a) and [Ni2@Ge17]4- (2a), are reported. The anions 1a and 2a, which close the gap between the known 16- and 18-atom Ge clusters, are investigated by single crystal X-ray diffraction and by quantum chemical calculations. The structures mark a new example on the pathway for cluster growth towards larger clusters with icosahedral symmetry. Furthermore, the [Co@Ge10]3- anion (3a) is obtained from liquid ammonia.

Intermetallic phases meet intermetalloid clusters.

In this article intermetalloid clusters of Cu-Zn, Cu-AI, Cu-Sn, and Cu-Pb are discussed. Intermetallic compounds based on these metal combinations are of the Hume-Rothery type with well-defined structures related to the valence electron count of the involved metals. Many Zintl-type and molecular clusters with these metals are known with remarkable structural parallels to the respective solid-state phases. On several examples, this article discusses intermetalloid clusters in terms of their metal core structures and relates them to structural principles in intermetallic solid-state phases. Also the syntheses of such clusters are addressed. Zintl-type and molecular clusters are most generally accessible from organometallic precursor complexes with redox processes between the different metals as an underlying synthesis concept.

Na7TaP4: A Ternary Sodium Phosphidotantalate Containing [TaP4]7- Tetrahedra.

While lithium phosphides have been investigated intensively, very little is known about the corresponding sodium-based phosphides. Here, we report on the first ternary Na-Ta-P compound Na7TaP4, which is easily accessible via ball milling of the elements and subsequent annealing. The single crystal X-ray structure determination [monoclinic symmetry; space group P21/c; and lattice parameters a = 11.5604(4), b = 8.1530(3), c = 11.5450(5) Å, and ß = 101.602(3)°] reveals [TaP4]7- tetrahedra, which are surrounded by Na+ counterions. Na7TaP4 crystallizes in a new structure type. The structure can be described as a strongly distorted hexagonal close packing of P atoms, in which the Ta atoms are located in tetrahedral voids, and Na atoms occupy all octahedral voids and additionally 3/8 of the tetrahedral voids. The possibility to increase the ion conductivity by changing the number of charge carriers through aliovalent substitution in compounds containing [SiP4]8- and [AlP4]9- is considered. The 31P and 23Na MAS NMR as well as the Raman spectra are in accordance with the structure model, and band structure calculations predict a direct band gap of 2.9 eV.

Crystal structure of strontium thio-sulfate monohydrate.

SrS2O3·H2O was obtained from an aqueous solution of Na2S2O3 and Sr(NO3)2 and crystallizes in space group P with all atoms at general positions. The Sr2+ ion exhibits an [8 + 1] coordination defined by two terminal S and six O atoms of thio-sulfate ions, one of the latter at a longer distance, and by one O atom of a water mol-ecule. Two thio-sulfate anions act as bidentate, four as monodentate ligands. The structure consists of mainly ionically inter-acting layers lying parallel to the crystallographic ab plane. The layers are connected by O-H⋯S and O-H⋯O hydrogen bonds of moderate strength.

Solvate-Induced Semiconductor to Metal Transition: Flat 1 ∞ [Bi1- ] Zigzag Chains in Metallic KBi⋠NH3 versus 1 ∞ [Bi1- ] Helices in Semiconducting KBi.

Polymeric 1 ∞ [Bi]- in KBi⋅NH3 has planar zigzag chains with two-connected Bi atoms and metallic properties, whereas KBi, which has helical chains of Bi atoms, is semiconducting. The isomerization of the Bi chain is induced by solvate molecules. In the novel layered solvate structure uncharged 2 ∞ [KBi] layers are separated by intercalated NH3 molecules. These layers are a structural excerpt of the iso(valence)electronic CaSi, whose metallic properties arise from the planarity of the zigzag chain of Si atoms. Computational studies support this view, they show an anisotropic metallic behavior along the Bi chain. Electron delocalization is also found in the new cyclic anion [Bi6 ]4- isolated in K2 [K(18-crown-6)]2 [Bi6 ]⋅9 NH3 . Although [Bi6 ]4- should exhibit one localized double bond, electron delocalization is observed in analogy to the lighter homologues [P6 ]4- and [As6 ]4- . Both compounds were characterized by single-crystal X-ray structure determination.

Crystal structures of the penta- and hexa-hydrate of thulium nitrate.

Tm(NO3)3·5H2O and Tm(NO3)3·6H2O, or more precisely [Tm(NO3)3(H2O)4]·H2O and [Tm(NO3)3(H2O)4]·2H2O, respectively, have been obtained from a concentrated solution of Tm2O3 in HNO3. The crystal structures of the two hydrates show strong similarities as both crystallize in space group P with all atoms at general positions and contain neutral, mol-ecular [Tm(NO3)3(H2O)4] complexes, i.e. ten-coordinated TmIII cations with three nitrate anions as bidentate ligands and four coordinating water mol-ecules, and one or two additional crystal water mol-ecules, respectively. All building units are connected by medium-strong to weak O-H⋯O hydrogen bonds. Tm(NO3)3·6H2O represents the maximally hydrated thulium nitrate as well as the heaviest rare earth nitrate hexa-hydrate known to date.

Fast Lithium Ion Conduction in Lithium Phosphidoaluminates.

Solid electrolyte materials are crucial for the development of high-energy-density all-solid-state batteries (ASSB) using a nonflammable electrolyte. In order to retain a low lithium-ion transfer resistance, fast lithium ion conducting solid electrolytes are required. We report on the novel superionic conductor Li9 AlP4 which is easily synthesised from the elements via ball-milling and subsequent annealing at moderate temperatures and which is characterized by single-crystal and powder X-ray diffraction. This representative of the novel compound class of lithium phosphidoaluminates has, as an undoped material, a remarkable fast ionic conductivity of 3 mS cm-1 and a low activation energy of 29 kJ mol-1 as determined by impedance spectroscopy. Temperature-dependent 7 Li NMR spectroscopy supports the fast lithium motion. In addition, Li9 AlP4 combines a very high lithium content with a very low theoretical density of 1.703 g cm-3 . The distribution of the Li atoms over the diverse crystallographic positions between the [AlP4 ]9- tetrahedra is analyzed by means of DFT calculations.

Silicon clusters with six and seven unsubstituted vertices via a two-step reaction from elemental silicon.

Unsaturated silicon clusters with only partial substitution, and thus, "naked" Si atoms are well studied species as they are proposed intermediates in gas-phase deposition processes. Although a remarkable number of stable molecular clusters has been reported, they are typically still obtained by multi-step syntheses. Herein we introduce a newly developed synthetic approach which led to the formation of the anionic species {Si(TMS)3}3Si9 - (1a) and {Si(TMS)3}2Si9 2- (1b), and an extension of this synthetic protocol resulted in the first covalent attachment of ligands through metal atoms to these clusters, (SnCy3)3Si9 - (2a) and (SnCy3)2Si9 2- (2b). The influence of the substituents on the electron localization in the central Si9 unit is analyzed by means of intrinsic bond orbital (IBO) analysis and partial atomic charge distribution. The IBO analyses reveal a new type of delocalization including 5-center-6-electron besides 3-center-2-electron bonds. The Raman spectra of 1b and 2b allow an assignment of the Si-Si intra-cluster vibrations by comparison to calculated (DFT-PBE0) spectra. The anions are formed in a one-step synthesis from binary K12Si17 which can easily be obtained by fusing the elements K and Si. The anions are characterized by ESI mass spectrometry and comprehensive NMR studies (1H, 13C, 29Si, 119Sn). Attempts to crystallize 1a and 2a as their (K-222crypt)+ salts yielded after the loss of one of the substituents single crystals containing 1b and 2b. The single crystal X-ray structure analyses reveal the presence of anionic siliconoids with surfaces of seven unsubstituted silicon atoms.

Early-Transition-Metal Complexes of Functionalized Nonagermanide Clusters: Synthesis and Characterization of [Cp2(MeCN)Ti(η1-Ge9{Si(TMS)3}3)] and K3[Cp2Ti(η1-Ge9{Si(TMS)3}2)2].

Anionic clusters with a homoatomic [Ge9] core are species with Ge atoms in low oxidation states. In this study their reaction with early-transition-metal complexes was investigated. We report the syntheses of Ti(III) complexes of silylated [Ge9] Zintl clusters, which are rare examples of molecular complexes with Ge-Ti interactions. The neutral species [Cp2(MeCN)Ti(η1-Ge9{Si(TMS)3}3)] (1) was obtained by the reaction of K[Ge9{Si(TMS)3}3] with [Cp2TiCl]2 in toluene as dark orange crystals, whereas the reaction of K2[Ge9{Si(TMS)3}2] with [Cp2TiCl]2 in thf and subsequent recrystallization from toluene resulted in dark green crystals of K3[Cp2Ti(η1-Ge9{Si(TMS)3}2)2] (2). Compound 2 contains the trianion [Cp2Ti(η1-Ge9{Si(TMS)3}2)2]3- (2a), which can be described either as a [Cp2Ti]+-bridged [Ge9{Si(TMS)3}2]2- dimer or as a heavily distorted tetrahedral Ti(III) complex bearing two germanide cluster ligands. Both compounds display donor-acceptor interactions between single Ge vertex atoms of the [Ge9] clusters and Ti(III). Compounds 1 and 2 were characterized by single-crystal X-ray diffraction, EPR spectroscopy, and elemental analysis.

Zinc as a versatile connecting atom for zintl cluster oligomers.

Homoatomic cluster aggregation is a versatile route to build up atom-precise nano structures. In this work we describe the first connection of four Ge9 clusters to a single atom: in K6[Zn{η1-Ge9(Hyp)2}4]·10.5 Tol four bis-silylated Ge9 clusters are linked via one central Zn atom. Furthermore we report on the bare Ge9 cluster in (NH3)3Zn-Ge9-Zn(NH3)3·11NH3, which reveals two possible connectivity sites due to the NH3 leaving groups at the Zn atoms. Both complexes can be regarded as analogue building motifs for hypothetical tetrel element structures anticipated before with Zn atoms taking the role of four-connected tetrel atoms.

Fast Ionic Conductivity in the Most Lithium-Rich Phosphidosilicate Li14SiP6.

Solid electrolytes with superionic conductivity are required as a main component for all-solid-state batteries. Here we present a novel solid electrolyte with three-dimensional conducting pathways based on "lithium-rich" phosphidosilicates with ionic conductivity of σ > 10-3 S cm-1 at room temperature and activation energy of 30-32 kJ mol-1 expanding the recently introduced family of lithium phosphidotetrelates. Aiming toward higher lithium ion conductivities, systematic investigations of lithium phosphidosilicates gave access to the so far lithium-richest compound within this class of materials. The crystalline material (space group Fm3m), which shows reversible thermal phase transitions, can be readily obtained by ball mill synthesis from the elements followed by moderate thermal treatment of the mixture. Lithium diffusion pathways via both tetrahedral and octahedral voids are analyzed by temperature-dependent powder neutron diffraction measurements in combination with maximum entropy method and DFT calculations. Moreover, the lithium ion mobility structurally indicated by a disordered Li/Si occupancy in the tetrahedral voids plus partially filled octahedral voids is studied by temperature-dependent impedance and 7Li NMR spectroscopy.

Metallocages for Metal Anions: Highly Charged [Co@Ge9 ]5- and [Ru@Sn9 ]6- Clusters Featuring Spherically Encapsulated Co1- and Ru2- Anions.

Endohedral clusters count as molecular models for intermetallic compounds-a class of compounds in which bonding principles are scarcely understood. Herein we report soluble cluster anions with the highest charges on a single cluster to date. The clusters reflect the close analogy between intermetalloid clusters and corresponding coordination polyhedra in intermetallic compounds. We now establish Raman spectroscopy as a reliable probe to assign for the first time the presence of discrete, endohedrally filled clusters in intermetallic phases. The ternary precursor alloys with nominal compositions "K5 Co1.2 Ge9 " and "K4 Ru3 Sn7 " exhibit characteristic bonding modes originating from metal atoms in the center of polyhedral clusters, thus revealing that filled clusters are present in these alloys. We report also on the structural characterization of [Co@Ge9 ]5- (1a) and [Ru@Sn9 ]6- (2a) obtained from solutions of the respective alloys.

Enhancing the Variability of [Ge9 ] Cluster Chemistry through Phosphine Functionalization.

The synthetic approach towards molecules that contain Ge atoms with oxidation state 0, and which are exclusively connected to other Ge atoms, is explored by using anionic clusters extracted from binary solids. Besides providing a novel variable method for the introduction of alkenyl moieties to [Ge9 ] cluster compounds, this work expands the spectrum of mixed-functionalized [Ge9 ] cluster anions, which are suitable for the straightforward synthesis of zwitterionic compounds upon coordination to metal cations. In detail, the synthesis of a series of mixed-functionalized [Ge9 ] clusters is reported, including [Ge9 {Si(TMS)3 }3 PRRI ] (R=tBu, RI =(CH2 )3 CH=CH2 ; 2) and [Ge9 {Si(TMS)3 }2 PRRI ]- (R and RI : alkyl, alkenyl, aryl, aminoalkyl; 3 a to 11 a, TMS: (trimethyl)silyl). In 2 and 3 a, pentenyl functionalization of the [Ge9 ] clusters was achieved by reaction of the novel chlorophosphine tBu{(CH2 )3 CH=CH2 }PCl (1) with silylated [Ge9 ] clusters. Furthermore, the reactivity of the cluster anions 3 a to 11 a towards NHCDipp MCl (NHCDipp =1,3-di(2,6-diisopropylphenyl)imidazolylidine; M=Cu, Ag) showed a dependency on the steric demand of the phosphine either zwitterions (3-MNHCDipp to 7-MNHCDipp ) featuring P-M interactions are formed, or Ge-M coordination (8-MNHCDipp to 11-MNHCDipp ) occurs. For M=Ag, the formation of zwitterionic complexes was unequivocally proven by NMR investigations showing 1 J(31 P-107 Ag/109 Ag) spin-spin coupling.

Silylated Ge9 Clusters as New Ligands for Cyclic (Alkyl)amino and Mesoionic Carbene Copper Complexes.

The coordination of Ge9 Zintl clusters at (carbene)CuI moieties is explored, and the complexes [(CAAC)Cu]2[η3-Ge9{Si(TMS)3}2] (1), (CAAC)Cu[η3-Ge9{Si(TMS)3}3] (2), and (MIC)Cu[η3-Ge9{Si(TMS)3}3] (3) are compared with their known N-heterocyclic carbene (NHC) derivatives (A and B), where CAAC = cyclic (alkyl)amino carbene, MIC = mesoionic carbene, and TMS = trimethylsilane. In analogy to the NHC derivatives, the synthesis of 1-3 proceeds by single-step reactions of (CAAC)CuCl or (MIC)CuCl with the [Ge9R2]2- and [Ge9R3]- [R = Si(TMS)3] cluster ligands, respectively, and yields complexes of (carbene)CuI (carbene = CAAC, MIC) moieties exhibiting η3-coordination modes of the Ge9 deltahedron to the Cu atom. In 1, [Ge9R2]2- acts as a η3-bridging unit for two (CAAC)CuI moieties, and 2 and 3 feature single (carbene)CuI (CAAC and MIC) fragments η3-connected to [Ge9R3]- units. Analysis of the bond lengths in comparison with known examples shows a bond expansion within the coordinated Ge3 triangular faces for all (carbene)CuIGe9 complexes (carbene = NHC, MIC, CAAC). All compounds are characterized by single-crystal X-ray diffractometry, NMR spectroscopy [1H, 13C{1H}, and 29Si{1H}], electrospray ionization mass spectometry, elemental analysis (C, H, and N), and for the first time also by IR and Raman investigations (for 2 and 3). The new complexes add to the known NHC derivatives and extend the exploration of Ge9 clusters with carbene ligands at CuI atoms.