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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Anionic Siliconoids from Zintl Phases: R3 Si9 - with Six and R2 Si9 2- with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)2 H).

Neutral and anionic silicon clusters (siliconoids) are regarded as important model systems for bulk silicon surfaces. For 25 years their formation from binary alkali metal silicide phases has been proposed, but experimentally never realized. Herein the silylation of a silicide, leading to the anionic siliconoids (Si(tBu)2 H)3 Si9 - (1 a) and (Si(tBu)2 H)2 Si9 2- (2 a) with the highest known number of ligand-free silicon atoms is reported for the first time. The new anions are obtained in a one-step reaction of K12 Si17 /NH3 (liq.) and Si(tBu)2 HCl/THF. Electrospray ionization spectrometry and 1 H, 13 C, 29 Si, as well as 29 Si-HMBC (heteronuclear multiple bond correlation) NMR spectroscopy, confirm the attachment of three silyl groups at a [Si9 ]4- cluster under formation of 1 a, in accordance with calculated NMR shifts. During crystal growth the siliconoid di-anion 2 a is formed. The single-crystal X-ray structure determination reveals that two silyl groups are connected to the deltahedral Si9 cluster core, revealing seven unsubstituted exposed silicon cluster atoms with a hemispheroidal coordination. The negative charges -1 and -2 are delocalized over the six and seven siliconoid Si atoms in 1 a and 2 a, respectively.

Acylation of Homoatomic Ge9 Cages and Subsequent Decarbonylation.

The direct acylation of Ge9 Zintl clusters by the reaction of K[Ge9 {Si(SiMe3 )3 }3 ] with acyl chlorides in hexane or toluene solutions is presented, leading to the neutral, carbonyl-derivatized products [{Si(SiMe3 )3 }3 Ge9 (CO)R'] (R'=Me, iPr, tBu, Ph, Bz, cyclopropylmethyl, phenethyl, 4-vinylphenyl). This reaction is applicable to a wide range of acyl chlorides and allows for diverse functionalization of Ge9 Zintl clusters. [{Si(SiMe3 )3 }3 Ge9 (CO)tBu] readily releases CO at ambient conditions under formation of [{Si(SiMe3 )3 }3 Ge9 tBu]. This temperature-dependent decarbonylation most likely proceeds via a radical Norrish-type I α-bond cleavage. Except for R'=tBu and Bz all obtained acyl-derivatized Ge9 cluster compounds do not release CO even at elevated temperatures. All compounds were characterized by NMR spectroscopy. [{Si(SiMe3 )3 }3 Ge9 (CO)R'] (R'=tBu, Ph, Me, iPr) as well as [{Si(SiMe3 )3 }3 Ge9 tBu] were further structurally characterized by single crystal X-ray diffraction.

Synthesis and Reactivity of Multiple Phosphine-Functionalized Nonagermanide Clusters.

Herein we report on the synthesis of the first multiple phosphine-substituted nonagermanide clusters in a one-step reaction from K4 Ge9 . Their reactions towards various transition metal complexes show a large variety of reactive sites. The novel threefold phosphine-functionalized [Ge9 ] clusters [Ge9 {PRRI }3 ]- {R: Ni Pr2 ; RI : Ni Pr2 (1 a) or t Bu (2 a)} are obtained by reaction of pristine [Ge9 ]4- clusters with the respective chlorophosphines. Subsequent reactions with NHCDipp CuCl yield neutral compounds (NHCDipp Cu)[Ge9 {P(Ni Pr2 )2 }3 ] (3) and (NHCDipp Cu)[Ge9 {P(Ni Pr2 )t Bu}3 ] (4), respectively. The reaction of neutral compound 3 with Cr(CO)5 (thf) yields the first uncharged fivefold substituted [Ge9 ] cluster (NHCDipp Cu)2 [Ge9 {P(Ni Pr2 )2 }2 Cr(CO)5 ] (5) via a ligand exchange reaction at the [Ge9 ] cluster core. Compounds 3 and 5 are characterized by single crystal structure determination.

Synthesis of Zintl Triads Comprising Extended Conjugated π-Electronic Systems: [RGe9-CH═CH-CH═CH-Ge9R]4- (R = -CH═CH2, -C(CH3)═CH-CH═N(CH2)2NH2).

Triads with extended conjugated π-electronic systems between polyhedral cage molecules possess promising electronic properties. In contrast to the known fullerene-bridge-fullerene triads, fewer synthetic procedures are known for the related homoatomic deltahedral cage molecules of the heavier homologues of carbon. The synthesis of the organo-Zintl triads [RGe9-CH═CH-CH═CH-Ge9R]4- with R = -CH═CH2 (R1), -C(CH3)═CH-CH═N(CH2)2NH2 ((2Z,4E)-7-amino-5-azahepta-2,4-dien-2-yl) (R2) is reported, in which the deltahedral Ge9 cages carry an additional functional group, allowing for further connections. Both anionic cage entities bear a butadiene-1,4-diyl bridge which is formed by reacting the Zintl ion [Ge9]4- with 1,4-bis(trimethylsilyl)butadiyne in ethylenediamine. The organic tethers can be attached by nucleophilic attack of the Ge9 clusters at the bis(trimethylsilyl)acetylene and (3Z/3E)-7-amino-1-(trimethylsilyl)-5-azahepta-3-en-1-yne, respectively, in ethylenediamine, and the products cis/trans-[R1Ge9-CH═CH-CH═CH-Ge9R1]4- and cis/cis-[R2Ge9-CH═CH-CH═CH-Ge9R2]4- have been isolated as [A(2,2,2-crypt)]+ salts with A = K, Rb, respectively. Crystals containing the novel anions [RGe9-CH═CH-CH═CH-Ge9R]4- have been structurally characterized by X-ray diffraction methods, and the compounds have been investigated by 1H and 13C NMR as well as by Raman spectroscopy. The cis/cis configurational isomer of [R1Ge9-CH═CH-CH═CH-Ge9R1]4- was characterized by means of NMR spectroscopy. Via in situ NMR measurements, we shed some light on the formation of the Zintl triads [RGe9-CH═CH-CH═CH-Ge9R]4- bearing supplemental organic tethers.

Synthesis and Characterization of the Lithium-Rich Phosphidosilicates Li10Si2P6 and Li3Si3P7.

The lithium phosphidosilicates Li10Si2P6 and Li3Si3P7 are obtained by high-temperature reactions of the elements or including binary Li-P precursors. Li10Si2P6 (P21/n, Z = 2, a = 7.2051(4) Å, b = 6.5808(4) Å, c = 11.6405(7) Å, ß = 90.580(4)°) features edge-sharing SiP4 double tetrahedra forming [Si2P6]10- units with a crystal structure isotypic to Na10Si2P6 and Na10Ge2P6. Li3Si3P7 (P21/m, Z = 2, a = 6.3356(4) Å, b = 7.2198(4) Å, c = 10.6176(6) Å, ß = 102.941(6)°) crystallizes in a new structure type, wherein SiP4 tetrahedra are linked via common vertices and which are further connected by polyphosphide chains to form unique ∞2[Si3P7]3- double layers. The two-dimensional Si-P slabs that are separated by Li atoms can be regarded as three covalently linked atoms layers: a defect α-arsenic type layer of P atoms sandwiched between two defect wurzite-type Si3P4 layers. The single crystal and powder X-ray structure solutions are supported by solid-state 7Li, 29Si, and 31P magic-angle spinning NMR measurements.

[SnBi3 ]5- -A Carbonate Analogue Comprising Exclusively Metal Atoms.

The new [SnBi3 ]5- polyanion is obtained by the reaction of K3 Bi2 with K4 Sn9 or K12 Sn17 in liquid ammonia. The anion is iso(valence)electronic with and structurally analogous to the carbonate ion. Despite the high negative charge of the anion, the Sn-Bi bond lengths range between single and double bonds. Quantum-chemical calculations at a DFT-PBE0/def2-TZVPP/COSMO level of theory reveal that the partial double bond character between the heavy main-group atoms Bi and Sn originates from a delocalized π-electronic system. The structure of the anion is determined by single-crystal X-ray diffraction analyses of the compounds K5 [SnBi3 ] 9 NH3 (1) and K9 [K(18-crown-6)][SnBi3 ]2 ⋅15 NH3 (2). The [SnBi3 ]5- unit is the first example of a carbonate-like anion obtained from solution, and it consists exclusively of metal atoms and completes the series of metal analogues of CO and CO2 .

Lithium Ion Mobility in Lithium Phosphidosilicates: Crystal Structure, 7 Li, 29 Si, and 31 P†MAS NMR Spectroscopy, and Impedance Spectroscopy of Li8 SiP4 and Li2 SiP2.

The need to improve electrodes and Li-ion conducting materials for rechargeable all-solid-state batteries has drawn enhanced attention to the investigation of lithium-rich compounds. The study of the ternary system Li-Si-P revealed a series of new compounds, two of which, Li8 SiP4 and Li2 SiP2 , are presented. Both phases represent members of a new family of Li ion conductors that display Li ion conductivity in the range from 1.15(7)×10-6 Scm-1 at 0 °C to 1.2(2)×10-4 Scm-1 at 75 °C (Li8 SiP4 ) and from 6.1(7)×10-8 Scm-1 at 0 °C to 6(1)×10-6 Scm-1 at 75 °C (Li2 SiP2 ), as determined by impedance measurements. Temperature-dependent solid-state 7 Li NMR spectroscopy revealed low activation energies of about 36 kJ mol-1 for Li8 SiP4 and about 47 kJ mol-1 for Li2 SiP2 . Both compounds were structurally characterized by X-ray diffraction analysis (single crystal and powder methods) and by 7 Li, 29 Si, and 31 P MAS NMR spectroscopy. Both phases consist of tetrahedral SiP4 anions and Li counterions. Li8 SiP4 contains isolated SiP4 units surrounded by Li atoms, while Li2 SiP2 comprises a three-dimensional network based on corner-sharing SiP4 tetrahedra, with the Li ions located in cavities and channels.

On the Nature of Bridging Metal Atoms in Intermetalloid Clusters: Synthesis and Structure of the Metal-Atom-Bridged Zintl Clusters [Sn(Ge9 )2 ]4- and [Zn(Ge9 )2 )]6.

The addition of Sn and Zn ions to [Ge9 ] clusters by reaction of [Ge9 ]4- with SnPh2 Cl2 , ZnCp*2 (Cp*=pentamethylcyclopentadienyl), or Zn2 [HC(Ph2 P=NPh)2 ]2 is reported. The resulting Sn- and Zn-bridged clusters [(Ge9 )M(Ge9 )]q- (M=Sn, q=4; M=Zn, q=6) display various coordination modes. The M atoms that coordinate to the open square of a C4v -symmetric [Ge9 ] cluster form strong covalent multicenter M-Ge bonds, in contrast to the M atoms coordinating to triangular cluster faces. Molecular orbital analyses show that the M atoms of the Ge9 M fragments coordinate to a second [Ge9 ] cluster with similar orbitals but in different ways. The [Ge9 Sn]2- unit donates two electrons to the triangular face of a second [Ge9 ]2- cluster with D3h symmetry, whereas [Ge9 Zn]2- acts as an electron acceptor when interacting with the triangular face of a D3h -symmetric [Ge9 ]4- unit.