[Ge9{Si(SiMe3)3}2{Ge(SiMe3)3}]–: The Mixed Substituted Metalloid Germanium Cluster and the Intermetalloid Cluster [ZnGe18{Si(SiMe3)3}4{Ge(SiMe3)3}2]

The novel metalloid germanium cluster [Ge₉(Hyp)₂Hyp^Ge]^– ( 1 ) was synthesized, exhibiting two different bulky groups [Hyp = Si(SiMe₃)₃; Hyp^Ge = Ge(SiMe₃)₃]. Further reaction of 1 with ZnCl₂ gives the derivative [ZnGe₁₈(Hyp)₄(Hyp^Ge)₂] ( 2 ) in good yield, showing that the substitution of Si(SiMe₃)₃ by Ge(SiMe₃)₃ within a metalloid Ge₉R₃^– compound leads to a comparable reactivity. 1 and 2 are characterized by NMR spectroscopy, mass spectrometry ( 1 ) and single crystal structure analyses ( 2 ). 1 and 2 are the first metalloid germanium clusters bearing germyl groups.     

Über die Kristallstrukturen der Cyanokomplexe [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O und [Cu(en)2][Ni(CN)4]

On the Crystal Structures of the Cyano Complexes [Co(NH₃)₆][Fe(CN)₆], [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O, and [Cu(en)₂][Ni(CN)₄] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH₃)₆][Fe(CN)₆] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH₃)₆][Co(CN)₆] type structure. [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H₂O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)₂][Ni(CN)₄] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.     

Studies on the Reactivity of [Ge9]4− towards [Fe(cot)(CO)3]: Synthesis and Characterization of [Ge8Fe(CO)3]3− and of the Anionic Organometallic Species [Fe(cot)(CO)3]−

Reaction of cyclooctatetraene (COT) iron(II) tricarbonyl, [Fe(cot)(CO)₃], with one equivalent of K₄Ge₉ in ethylenediamine (en) yielded the cluster anion [Ge₈Fe(CO)₃]^3? which was crystallographically‐characterized as a [K(2,2,2‐crypt)]⁺ salt in [K(2,2,2‐crypt)]₃[Ge₈Fe(CO)₃]. The chemically‐reduced organometallic species [Fe(η³‐C₈H₈)(CO)₃]^? was also isolated as a side‐product from this reaction as [K(2,2,2‐crypt)][Fe(η³‐C₈H₈)(CO)₃]. Both species were further characterized by EPR and IR spectroscopy and electrospray mass spectrometry. The [Ge₈Fe(CO)₃]^3? cluster anion represents an unprecedented functionalized germanium Zintl anion in which the nine‐atom precursor cluster has lost a vertex, which has been replaced by a transition‐metal moiety.     

The Largest Metalloid Group 14 Cluster,Ge18[Si(SiMe3)3]6: An Intermediate on the Way to Elemental Germanium

The oxidation of [Ge₉(Hyp)₃]^? (Hyp=Si(SiMe₃)₃) with an Fe^II salt leads to Ge₁₈(Hyp)₆ ( 1 ), the largest Group 14 metalloid cluster that has been structurally characterized to date. The arrangement of the 18 germanium atoms in 1 shows similarities to that found in the solid‐state structure Ge(cF136). Furthermore, 1 can be described as a macropolyhedral cluster of two Ge₉ units. Quantum‐chemical calculations further hint at a strained arrangement so that 1 can be considered as a first trapped intermediate on the way from Ge₉ units to elemental germanium with the clathrate‐II structure (Ge(cF136)).     

Magnetocaloric Properties of Heterometallic 3d–Gd Complexes Based on the [Gd(oda)3]3− Metalloligand

A series of heterometallic 3d–Gd³⁺ complexes based on a lanthanide metalloligand, [M(H₂O)₆][Gd(oda)₃] ? 3 H₂O [M=Cr³⁺ ( 1‐Cr )] (H₂oda=2,2′‐oxydiacetic acid), [M(H₂O)₆][MGd(oda)₃]₂ ? 3 H₂O [M=Mn²⁺ ( 2‐Mn ), Fe²⁺ ( 2‐Fe ) and Co²⁺ ( 2‐Co )], and [M₃Gd₂(oda)₆(H₂O)₆] ? 12 H₂O [M=Ni²⁺ ( 3‐Ni ), Cu²⁺ ( 3‐Cu ), and Zn²⁺ ( 3‐Zn )], are reported. Magnetic and heat‐capacity studies revealed a significant impact on the magnetocaloric effect depending on the anisotropy of the 3d transition metal ions, as confirmed by comparison of the observed maximum values of ?ΔS_m between complexes 2‐Co and 1‐Cr . In these two complexes, the 3d metal ions have the same spin (S=3/2 for Co²⁺ and Cr³⁺ ions), and the theoretical calculation suggested a larger ?ΔS_m value for 2‐Co (47.8 J K^?1 kg^?1) than 1‐Cr (37.5 J K^?1 kg^?1); however, the significant anisotropy of Co²⁺ ions in 2‐Co , which can result in smaller effective spins, gives a smaller value of ?ΔS_m for 2‐Co (32.2 J K^?1 kg^?1) than for 1‐Cr (35.4 J K^?1 kg^?1) at ΔH=9 T.     

Derivate des Flußspat-Typs: [Fe(NH3)6][TaF6]2 und [Ni(NH3)6][TaF6]2

Derivatives of the Fluorite Type: [Fe(NH₃)₆][TaF₆]₂ and [Ni(NH₃)₆][TaF₆]₂ Light blue single crystals of [Fe(NH₃)₆][TaF₆]₂ and [Ni(NH₃)₆][TaF₆]₂ are obtained from 36 : 1 : 6 molar mixtures of (NH₄)F, iron/nickel and tantalum powders, respectively, in sealed Monel metal ampoules at 400 °C. They both crystallize isotypic with [Co(NH₃)₆][PF₆]₂ (cubic, Fm-3m, Z = 4, a = 1259.0(2)/1260.4(2) pm) in a structure that can be derived from the basic fluorite-type of structure according to [Ca][F]₂≡[Fe(NH₃)₆][TaF₆]₂, for example.     

The Arene‐Stabilized η5‐Pentamethylcyclopentadienyl Arsenic Dication [(η5‐Cp*)As(toluene)]2+

Double chloride abstraction of Cp*AsCl₂ gives the dicationic arsenic species [(η⁵‐Cp*)As(tol)][B(C₆F₅)₄]₂ ( 2 ) (tol=toluene). This species is shown to exhibit Lewis super acidity by the Gutmann–Beckett test and by fluoride abstraction from [NBu₄][SbF₆]. Species 2 participates in the FLP activation of THF affording [(η²‐Cp*)AsO(CH₂)₄(THF)][B(C₆F₅)₄]₂ ( 5 ). The reaction of 2 with PMe₃ or dppe generates [(Me₃P)₂As][B(C₆F₅)₄] ( 6 ) and [(σ‐Cp*)PMe₃][B(C₆F₅)₄] ( 7 ), or [(dppe)As][B(C₆F₅)₄] ( 8 ) and [(dppe)(σ‐Cp*)₂][B(C₆F₅)₄]₂ ( 9 ), respectively, through a facile cleavage of C?As bonds, thus showcasing unusual reactivity of this unique As‐containing compound.     

Synthesis and Crystal Structure of the two Lithium Hypersilylcuprates LiCu2[Si(SiMe3)3]3 and [Li7(OtBu)6][Cu2{Si(SiMe3)3}3]

The two hypersilylcuprates LiCu₂Hyp₃ ( 2 ) and [Li₇(O^tBu)₆][Cu₂Hyp₃] ( 3 ) (Hyp = Si(SiMe₃)₃) were synthesized by reactions of unsolvated lithium hypersilanide, LiHyp with hypersilylcopper and CuO^tBu, respectively. Both contain the novel A‐frame trihypersilyldicuprate anion [Cu₂Hyp₃]^–. In the former case a molecular compound is produced containing intimate ion pairs. In the latter case the cuprate anion and the unique large [Li₇(O^tBu)₆]⁺ cation form a salt‐like compound, only sparingly soluble in unpolar solvents. According to NBO analyses the bonding within the trihypersilyldicuprate moiety is best described by interaction of a bridging lewis‐basic hypersilanide anion with two lewis‐acidic hypersilyl copper fragments.     

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 SnPh₂Cl₂, ZnCp*₂ (Cp*=pentamethylcyclopentadienyl), or Zn₂[HC(Ph₂P=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 C_4v‐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 Ge₉M fragments coordinate to a second [Ge₉] cluster with similar orbitals but in different ways. The [Ge₉Sn]^2?unit donates two electrons to the triangular face of a second [Ge₉]^2? cluster with D_3h symmetry, whereas [Ge₉Zn]^2?acts as an electron acceptor when interacting with the triangular face of a D_3h‐symmetric [Ge₉]^4? unit.     

Oxidative Coupling of Ge94‐ Zintl Anions ‐ Hexagonal Rod Packing of Linear [Ge9=Ge9=Ge9=Ge9]8‐

The compound [K(18‐crown‐6)]₈[Ge₉=Ge₉=Ge₉=Ge₉] ˙ 8en ( 1 ) featuring a [Ge₉=Ge₉=Ge₉=Ge₉]^8‐cluster anion was synthesized from K₄Ge₉ for the first time. The X‐ray single crystal analysis shows that, in many respects such as bond connection and packing style, compound 1 is quite different from the previously reported compounds [Rb(18‐crown‐6)]₈[Ge₉=Ge₉=Ge₉=Ge₉] ˙ 2en ( 2 ) and [Rb(18‐crown‐6)]₈[Ge₉=Ge₉=Ge₉=Ge₉] ˙ 6en ( 3 ). Crystal packing of 1 gives strong indications that the highly charged nano‐rods self assembly in a hexagonal rod packing.     

Untersuchungen zur Sb–Sb‐Bindungsknüpfung in der Koordinationssphäre von Übergangsmetallen

Investigations of Sb–Sb Bond Formation Reactions in the Coordination Sphere of Transition Metals The reaction of SbCl₃ with various transition metal metalates of the type K[ML_n] [ML_n = Ni(CO)Cp*, Fe(CO)Cp′, Co(CO)₄; Cp* = η⁵‐C₅Me₅, Cp′ = η⁵‐C₅H₄Me] in the presence of [Cr(CO)₅thf] have been studied. With K[Ni(CO)Cp*] and K[Fe(CO)₂Cp′] the trigonal‐pyramidal complexes [(μ₃‐Sb){Ni(CO)Cp*}₃] ( 1 ) and [(μ₃‐Sb){Fe · (CO)₂Cp′}₃] ( 2 ), respectively, are obtained. The reaction with K[Co(CO)₄] leads to the tetrahedral cluster [Co₃(CO)₉(μ₃‐Sb{Cr(CO)₅})] ( 3 ) and the butterfly cluster [Co₂(CO)₆(μ‐SbCl)(μ‐SbCl{Cr(CO)₅})] ( 4 ). All products are characterised by X‐ray crystal structure determination. In contrast to the corresponding [(CO)₅CrPCl₃] system forming P–P bonds, starting from SbCl₃/[Cr(CO)₅thf] does not cause a Sb–Sb bond formation.     

On the Reactivity of Silylated Ge9 Clusters: Synthesis and Characterization of [ZnCp*(Ge9{Si(SiMe3)3}3)], [CuPiPr3(Ge9{Si(SiMe3)3}3)], and [(CuPiPr3)4{Ge9(SiPh3)2}2]

We report on the synthesis of new derivatives of silylated clusters of the type [Ge₉(SiR₃)₃]^? (R = SiMe₃, Me = CH₃; R = Ph, Ph = C₆H₅) as well as on their reactivity towards copper and zinc compounds. The silylated cluster compounds were synthesized by heterogeneous reactions starting from the Zintl phase K₄Ge₉. Reaction of K[Ge₉{Si(SiMe₃)₃}₃] with ZnCl₂ leads to the already known dimeric compound [Zn(Ge₉{Si(SiMe₃)₃}₃)₂] ( 1 ), whereas upon the reaction with [ZnCp*₂] the coordination of [ZnCp*]⁺ to the cluster takes place (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) under the formation of [ZnCp*(Ge₉{Si(SiMe₃)₃}₃)] ( 2 ). A similar reaction leads to [CuPiPr₃(Ge₉{Si(SiMe₃)₃}₃)] ( 3 ) from [CuPiPr₃Cl] (iPr=isopropyl). Further we investigated the novel silylated cluster units [Ge₉(SiPh₃)₃]^? ( 4 ) and [Ge₉(SiPh₃)₂]^? ( 5 ), which could be identified by mass spectroscopy. Bis‐ and tris‐silylated species can be synthesized by the respective stoichiometric reactions, and the products were characterized by ESI‐MS and NMR experiments. These clusters show rather different reactivity. The reaction of the tris‐silylated anion 4 with [CuPiPr₃Cl] leads to [(CuPiPr₃)₃Ge₉(SiPh₃)₂]⁺ as shown from NMR experiments and to [(CuPiPr₃)₄{Ge₉(SiPh₃)₂}₂] ( 6 ), which was characterized by single‐crystal X‐ray diffraction. Compound 6 shows a new type of coordination of the Cu atoms to the silylated Zintl clusters.     

Decamethyl­ferrocenium bis­(2‐oxo‐1,3‐dithiole‐4,5‐dithiolato‐κ2S4,S5)nickelate(III) tetra­hydro­furan solvate

The title compound, [Fe(C₁₀H₁₅)₂][Ni(C₃OS₄)₂]·C₄H₈O or [Fe(Cp*)₂][Ni(dmio)₂]·THF, where [Fe(Cp*)₂]⁺ is the deca­methyl­ferrocenium cation, dmio is the 2‐oxo‐1,3‐dithiole‐4,5‐dithiol­ate dianion and THF is tetra­hydro­furan, crystallizes with two independent half‐anion units [one Ni atom is at the centre of symmetry (, , 0) and the other is at the centre of symmetry (, 0, )], one cation unit (located in a general position) and one THF solvent mol­ecule in the asymmetric unit. The crystal structure consists of two‐dimensional layers composed of parallel mixed chains, where pairs of cations alternate with single anions. These layers are separated by sheets of anions and THF mol­ecules.     

Functionalization of [Ge9] with Small Silanes:[Ge9(SiR3)3]– (R = iBu,iPr, Et) and the Structures of (CuNHCDipp)[Ge9{Si(iBu)3}3], (K‐18c6)Au[Ge9{Si(iBu)3}3]2, and (K‐18c6)2[Ge9{Si(iBu)3}2]

Novel silylation reactions at [Ge₉] Zintl clusters starting from the chlorosilanes SiR₃Cl (R = iBu, iPr, Et) and the Zintl phase K₄Ge₉ are reported. The formation of the tris‐silylated anions [Ge₉(SiR₃)₃]^– [R = iBu ( 1a ), iPr ( 1b ), Et ( 1c )] by heterogeneous reactions in acetonitrile was monitored by ESI‐MS measurements. For R = iBu ¹H, ¹³C and ²⁹Si NMR experiments confirmed the exclusive formation of 1a . Subsequent reactions of 1a with CuNHC^DippCl and Au(PPh₃)Cl result in formation of the neutral metal complex (CuNHC^Dipp)[Ge₉{Si(iBu)₃}₃]·0.5 tol ( 2 ·0.5 tol) and the metal bridged dimeric unit {Au[Ge₉{Si(iBu)₃}₃]₂}^– ( 3a ), isolated as a (K‐18c6)⁺ salt in (K‐18c6)Au[Ge₉{Si(iBu)₃}₃]₂·tol ( 3 ·tol), respectively. Finally, from a toluene/hexane solution of 1a in presence of 18‐crown‐6, crystals of the compound (K‐18c6)₂[Ge₉{Si(iBu)₃}₂]·tol ( 4 ·tol), containing the bis‐silylated cluster anion [Ge₉(Si(iBu)₃)₂]^2– ( 4a ), were obtained. The compounds 2 ·0.5 tol, 3 ·tol and 4 ·tol were characterized by single‐crystal structure determination.     

σ‐Aromaticity‐Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4− and [Cd6Ge16]4−

In this work, the largest heterometallic supertetrahedral clusters, [Zn₆Ge₁₆]^4? and [Cd₆Ge₁₆]^4?, were directly self‐assembled through highly‐charged [Ge₄]^4? units and transition metal cations, in which 3‐center–2‐electron σ bonding in Ge₂Zn or Ge₂Cd triangles plays a vital role in the stabilization of the whole structure. The cluster structures have an open framework with a large central cavity of diameter 4.6 Å for Zn and 5.0 Å for Cd, respectively. Time‐dependent HRESI‐MS spectra show that the larger clusters grow from smaller components with a single [Ge₄]^4? and ZnMes₂ units. Calculations performed at the DFT level indicate a very large HOMO–LUMO energy gap in [M₆Ge₁₆]^4? (2.22 eV), suggesting high kinetic stability that may offer opportunities in materials science. These observations offer a new strategy for the assembly of heterometallic clusters with high symmetry.     

Functionalization of Pentaphosphorus Cations by Complexation

The chemistry of polyphosphorus cations has rapidly developed in recent years, but their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P₅R₂]⁺ cations with cyclopentadienyl metal complexes. The reaction of [Cp^ArFe(μ‐Br)]₂ (Cp^Ar=C₅(C₆H₄‐4‐Et)₅) with [P₅R₂][GaCl₄] (R=iPr and 2,4,6‐Me₃C₆H₂ (Mes)) afforded bicyclo[1.1.0]pentaphosphanes ( 1‐R , R=iPr and Mes), showing an unsymmetric “butterfly” structure. The same products 1‐R were formed from K[Cp^Ar] and [P₅R₂][GaCl₄]. The cationic complexes [Cp^ArCo(η⁴‐P₅R₂)][GaCl₄] ( 2‐R [GaCl₄], R=iPr and Cy) and [(Cp^ArNi)₂(η^3:3‐P₅R₂)][GaCl₄] ( 3‐R [GaCl₄]) were obtained from [P₅R₂][GaCl₄] and [Cp^ArM(μ‐Br)]₂ (M=Co and Ni) as well as by using low‐valent “Cp^ArM^I” sources. Anion metathesis of 2‐R [GaCl₄] and 3‐R [GaCl₄] was achieved with Na[BArF₂₄]. The P₅ framework of the resulting salts 2‐R [BArF₂₄] can be further functionalized with nucleophiles. Thus reactions with [Et₄N]X (X=CN and Cl) give unprecedented cyano‐ and chloro‐functionalized complexes, while organo‐functionalization was achieved with CyMgCl.     

Tuning the Magnetization Dynamic Properties of Nd⋅⋅⋅Fe and Nd⋅⋅⋅Co Single‐Molecular Magnets by Introducing 3 d–4 f Magnetic Interactions

By using paramagnetic [Fe(CN)₆]^3? anions in place of diamagnetic [Co(CN)₆]^3? anions, two field‐induced mononuclear single‐molecular magnets, [Nd(18‐crown‐6)(H₂O)₄][Co(CN)₆] ? 2 H₂O ( 1 ) and [Nd(18‐crown‐6)(H₂O)₄][Fe(CN)₆] ? 2 H₂O ( 2 ), have been synthesized and characterized. Single‐crystal X‐ray diffraction analysis revealed that compounds 1 and 2 were ionic complexes. The Nd^III ions were located inside the cavities of the 18‐crown‐6 ligands and were each bound by four water molecules on either side of the crown ether. Magnetic investigations showed that these compounds were both field‐induced single‐molecular magnets. By comparing the slow relaxation behaviors of compounds 1 and 2 , we found significant differences between the direct and Raman processes for these two complexes, with a stronger direct process in compound 2 at low temperatures. Complete active space self‐consistent field (CASSCF) calculations were also performed on two [Nd(18‐crown‐6)(H₂O)₄]³⁺ fragments of compounds 1 and 2 . Ab initio calculations showed that the magnetic anisotropies of the Nd^III centers in complexes 1 and 2 were similar to each other, which indicated that the difference in relaxation behavior was not owing to the magnetic anisotropy of Nd^III. Our analysis showed that the magnetic interaction between the Nd^III ion and the low‐spin Fe^III ion in complex 2 played an important role in enhancing the direct process and suppressing the Raman process of the single‐molecular magnet.     

A Series of Novel Organically Templated Germanium Antimony Sulfides

A series of novel organically templated germanium antimony sulfides have been solvothermally synthesized and structurally, thermally, and optically characterized. The compound [Me₂NH₂]₆[(Ge₂Sb₂S₇)(Ge₄S₁₀)] ( 1 ) features two distinct tetranuclear [Ge₂Sb₂S₇]^2? and [Ge₄S₁₀]^4? isolated clusters. The compound [(Me)₂NH₂][DabcoH]₂[Ge₂Sb₃S₁₀] ( 2 ) (Dabco=triethylenediamine) features a 1D‐[Ge₂Sb₃S₁₀]_n^3n? ribbon constructed with two [GeSbS₅]_n^3n? chains bridged by Sb³⁺ ion in ψ‐SbS₄ configuration. Compounds [M(en)₃][GeSb₂S₆] (M=Ni ( 3 ), Co ( 4 ) en=ethylenediamine) feature the unique 2D grid layer structures of [GeSb₂S₆]_n^2n?. The compound [(Me)₂NH₂]₂[GeSb₂S₆] ( 5 ) previously reported by us features a 3D chiral microporous structure with the chiral channels. The optical absorption spectra indicate that all the compounds are wide bandgap semiconductors. Thermal stabilities of these compounds have been investigated by thermogravimetric analyses (TGA).     

Thermolyse von Cyanokomplexen. VII. Über die Thermischen Zersetzungsreaktionen der Hexacyanokobalte(III); Ligandenumlagerungen bei der Thermolyse

Thermolysis of cyano complexes. VII. On the thermal decomposition of hexacyanocobaltate(III); ligand exchange during thermolysis The thermal decomposition of hexacyanocobaltates(III) yields, as products of successive intramolecular redox reactions, first dicyan and Co^II(Co^III)-complexes, then Co^II[Co^II]-complexes and simple Co^II(CN)₂, respectively, and finally Co^ICN and elemental Co, respectively. All the compounds of the [Co^III(NH₃)₆]³⁺ cation with the cyanometallate anions of Co, Fe, Cr, Mn, Ni, Mo yield the same DTA curve as [Co(NH₃)₆][Co(CN)₆] does; in the case of Ni and Cr, which are capable of forming ammine complexes, simultaneous mutual ligand exchange occurs.     

Germanates of 1D Chains, 2D Layers,and 3D Frameworks Built from Ge–O Clusters by Using Metal‐Complex Templates: Host–Guest Symmetry and Chirality Transfer

The self‐assembly of Ge–O polyhedra by metal‐complex templates leads to initial examples of open germanate structures under mild solvothermal conditions. These materials are constructed from Ge–O cluster building bocks (Ge₇X₁₉ (X=O, OH, or F) or Ni@Ge₁₄O₂₄(OH)₃) and span the full range of dimensionalities from 1D chains of Ge₇O₁₃(OH)₂F₃?Cl?2[Ni(dien)₂] (FJ‐ 6 ) to 2D layers of Ge₇O₁₄F₃?0.5[In(dien)₂]?0.5H₃dien? 2H₂O ( 1 ) and 3D frameworks of Ni@ Ge₁₄O₂₄(OH)₃?2[Ni(L)₃] (FJ‐ 1 a /FJ‐ 1 b ) (dien=diethylenetriamine, L=ethylenediamine (en) or 1,2‐diaminopropane (enMe)). The Ge₇X₁₉ cluster in FJ‐ 6 and 1 is formed by condensation of four GeX₄ tetrahedra, two GeX₅ trigonal bipyramids, and one GeX₆ octahedron with a μ₃‐O atom at the center of the cluster, whereas the Ni@ Ge₁₄O₂₄(OH)₃ cluster in FJ‐ 1 a /FJ‐ 1 b is formed by condensation of nine peripheral GeO₄ tetrahedra and five interior GeO₃Ni units with one μ₅‐Ni atom at the center of the cluster. FJ‐ 6 is characterized by a pair of racemic Ge₇O₁₄(OH)₂F₃ cluster chains and represents only one example of 1D germanates; 1 exhibits unique germanate layers with uniform 10‐membered‐ring apertures encapsulating an unknown indium complex, and the framework structure of FJ‐ 1 a /FJ‐ 1 b with large 24‐membered‐ring channels is the first example of porous materials that contain metal–metal bonds (Ge²⁺? Ni⁺). These initial examples of germanates from metal‐complex templates provide a useful model system for understanding the mechanisms of host–guest interactions, which may further facilitate the design and development of new porous materials “on demand”. It is shown that the symmetry and configuration of the guest metal complex can be imprinted onto the host inorganic framework through hydrogen bonding between host and guest.