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1.
Summary. New selenidogermanates [Mn(en)3]2Ge2Se6 (en = ethylenediamine) and [Fe(dien)2]2Ge2Se6 (dien= diethylenetriamine) were synthesized by the reaction of germanium dioxide, elemental selenium, and transition metal chlorides in respectively en and dien. Both compounds crystallize in the monoclinic space group P21/n with two formula units in the unit cell, and consist of discrete [Ge2Se6]4− anions with transition metal complex cations as counter ions. The [Ge2Se6]4− anion is formed by two GeSe4 tetrahedra sharing a common edge to form a planar Ge2Se2 four-membered ring. The [Mn(en)3]2+ and [Ni(dien)2]2+ complex cations are in distorted octahedral geometry. In both selenidogermanates extensive N–H···Se hydrogen bonding contacts lead to 3-dimensional network structures. The band gaps of 2.36 and 2.25 eV were derived from optical absorption spectra. Thermogravimetric analysis shows that the first compound decomposes in two steps under the nitrogen stream, while the second exhibits a one-step decomposition process.  相似文献   

2.
A series of lanthanide selenidogermanates (H3O)[Tm(teta)2][Ge2Se6] (1, teta = triethylenetetramine) and [Ln(teta)(tren)Cl]2[Ge2Se6](en) {en = ethylenediamine, tren = N,N,N- tris(2-aminoethyl)amine, Ln = Pr (2a), Nd (2b), Sm (2c), Eu (2d), Gd (2e), Tb (2f)}were prepared under mild solvothermal conditions and structurally characterized. 1 contains isolated [Tm(teta)2]3+ ions, protonated H3O+ ions and dimeric [Ge2Se6]4? anions, while 2af are composed of [Ln(teta)(tren)Cl]3+ ions, dimeric [Ge2Se6]4? anions and free en molecules. The lighter lanthanide ions (Pr–Tb) adopt a distorted tricapped trigonal prism with the nine-coordinated number, and the heavier Tm3+ ion adopts a distorted bicapped trigonal prism with the eight-coordinated number. Their band gaps in the range of 1.52–1.86 eV are derived from optical absorption spectra.  相似文献   

3.
The lanthanide selenidogermanates [{Eu(en)3}2(μ‐OH)2]Ge2Se6 ( 1 ), [{Ho(en)3}2(μ‐OH)2]Ge2Se6 ( 2 ), and [{Ho(dien)2}2(μ‐OH)2]Ge2Se6 ( 3 ) (en = ethylenediamine, dien = diethylenetriamine) were solvothermally prepared by the reactions of Eu2O3 (or Ho2O3), germanium, and selenium in en and dien solvents respectively. Compounds 1 – 3 are composed of selenidogermanate [Ge2Se6]4– anion and dinuclear lanthanide complex cation [{Ln(en)3}2(μ‐OH)2]4+ (Ln = Eu, Ho) or [{Ho(dien)2}2(μ‐OH)2]4+. The [Ge2Se6]4– anion is composed of two GeSe4 tetrahedra sharing a common edge. The dinuclear lanthanide complex cations are built up from two [Ln(en)3]3+ or [Ho(dien)2]3+ ions joined by two μ‐OH bridges. All lanthanide(III) ions are in eight‐coordinate environments forming distorted bicapped trigonal prisms. In 1 – 3 , three‐dimensional supramolecular networks of the anions and cations are formed by N–H ··· Se and N–H ··· O hydrogen bonds. To the best of our knowledge, 1 – 3 are the first examples of selenidogermanate salts with lanthanide complex counter cations.  相似文献   

4.
The title compound, [Zn(C2H3O2)(C6H18N4)][B5O6(OH)4], contains mixed‐ligand [Zn(CH3COO)(teta)]+ complex cations (teta is triethylenetetramine) and pentaborate [B5O6(OH)4] anions. The [B5O6(OH)4] anions are connected to one another through hydrogen bonds, forming a three‐dimensional supramolecular network, in which the [Zn(CH3COO)(teta)]+ cations are located.  相似文献   

5.
The compound [K([2.2.2]crypt)]Cs7[Sn9]2(en)3 ( 1 ) was synthesized from an alloy of formal composition KCs2Sn9 by dissolving in ethylenediamine (en) followed by the addition of [2.2.2]crypt and toluene. 1 crystallizes in the orthorhombic space group Pcca with a = 45.38(2), b = 9.092(4), c = 18.459(8) Å, and Z = 4. The structure consists of Cs7[Sn9]2 layers which contain [Sn9]4– anions and Cs+ cations. The layers are separated by [K([2.2.2]crypt)]+ units. In the intermetallic slab (Cs7[Sn9]2) compares the arrangement of pairs of symmetry‐related [Sn9]4– anions with the dimer ([Ge9]–[Ge9])6– in [K([2.2.2]crypt)]2Cs4([Ge9]–[Ge9]), in which the clusters are linked by a cluster‐exo bond. The shortest distance between atoms of such two clusters in 1 is 4.762 Å, e. g. there are no exo Sn‐Sn bonds. The [Sn9]4– anion has almost perfect C4v‐symmetry.  相似文献   

6.
Two new indium selenides [In(en)2Se]2·2I ( 1 ) and [In(teta)Se]2·2I ( 2 ) (en = ethylenediamine, teta = triethylenetetramine) were obtained under mild solvothermal conditions and structurally characterized. Compounds 1 and 2 consist of unusual organic hybrid indium selenide cations and I? anions. These ions are assembled to two different supramolecular structures by N‐H···I and N‐H···Se H‐bonds, namely extended 3‐D network structure for 1 and extended sheet structure for 2 . The optical band gaps of 2.92 eV for 1 and 3.15 eV for 2 were derived from optical absorption spectra. The thermal stability of 1 and 2 was investigated by thermogravimetric measurements.  相似文献   

7.

Abstract  

Two new transition-metal thiogermanates [M(dap)3]4Ge4S10Cl4 (M = Co, Ni; dap = 1,2-propanediamine) have been solvothermally synthesized and structurally characterized. The two thiogermanates are isostructural and consist of discrete Ge4S104− adamantane-like ions, free Cl ions, and [M(dap)3]2+ cations as counterions. The Ge4S104− anion is built from corner-sharing connection of four GeS44− tetrahedra. Although some chalcogenidogermanates have been obtained by use of in situ generated transition-metal complexes as structure-directing agents under mild solvothermal conditions, their anions are usually dimeric [Ge2Q6]4− (Q = S, Se) species. The new thiogermanates are rare examples of adamantane-like (Ge4S104−) thiogermanates combined with transition-metal complexes. Their optical properties have been investigated by UV–Vis spectra.  相似文献   

8.
本文总结了软化学方法合成有机杂化的锗、锡硫属化合物的研究进展,介绍了代表性物质的结构以及[M2Q6]4-、[M3Q7]2-、[M4Q9]2-、[M4Q10]4-(M=Ge,Sn;Q=S,Se,Te)等构筑单元的超分子组装、聚合过程中的主要影响因素。  相似文献   

9.
Two new 1-D lanthanide selenidogermanates [Ln2(tepa)2(μ-OH)2(μ-Ge2Se6)]n·xnH2O (Ln = Tb (1), x = 0.5; Ln = Tm (2), x = 0; tepa = tetraethylenepentamine) have been solvothermally synthesized and structurally characterized. Compounds 1 and 2 contain 1-D polymeric chains [Ln2(tepa)2(μ-OH)2(μ-Ge2Se6)]n constructed by a [Ge2Se6]4? anion as a bridging ligand with trans terminal Se atoms linking [Ln2(μ-OH)2(tepa)2]4+ complex cations, but the stacking patterns of these neutral chains are different. The 1-D chains of 1 are alternately stacked in a crossing manner, while the infinite chains of 2 are arranged in a parallel manner. Although a few lanthanide selenidogermanates containing the [Ge2Se6]4? anion have been reported, their [Ge2Se6]4? anions are usually discrete. Compounds 1 and 2 provide the rare example of [Ge2Se6]4? anion as a bridging ligand to a lanthanide complex cation. Their optical and magnetic properties have also been studied.  相似文献   

10.
The new chalcogenido ortho indates(III) K5[InSe4] and K12[InS4]2(S) were synthesized from melts of the elements (Se) [or with S/In2S3 as chalcogen source] at maximum temperatures of 700/800 °C. The two potassium salts, which were characterized by means of X-ray single crystal structure analysis, contain isolated tetrahedral ortho anions [InQ4]5–. K5[InSe4] crystallizes in a new structure type [monoclinic, space group C2/c, a = 2014.2(2), b = 1553.1(2), c = 1661.1(2) pm, β = 94.716(2)°, Z = 16, R1 = 0.0317]. The complex structure contains two crystallographically different [InSe4]5– tetrahedra [d(In ··· Se) = 254.3–263.6 pm], which are arranged into 44 [In(1), A ] and 32.4.3.4 [In(2), B ] nets. These nets are |: ABA ' B ':| stacked along the a axis. The 11 crystallographically independent K+ ions are coordinated by four (1×), five (3×) and six (7×) selenido anions [d(K–Se) = 309–415 pm]. The crystal structure and the calculated electronic structure of the pure ortho indate K5[InSe4] are compared with the known “double salts” K9[InSe4]2(Se) and K9[InSe4](Se2)(Se), which exhibit selenide (and diselenide) anions in addition to the ortho metallate. Similarly, the new sulfido indate K11[InS4]2(S) contains sulfide anions besides the indate tetrahedra. In the chiral structure (K6[InTe4](Cl)-type, hexagonal, space group P63mc, a = 1026.22(10), c = 752.34(7) pm, Z = 2, R1 = 0.0332) layers of similarly oriented [InS4] tetrahedra [d(In ··· Se) = 246.6/248.1 pm] are hexagonally |: AB :| stacked along one threefold axis. The additional sulfide anions are centered in K+ octahedra. In contrast to the isotypic chloride, only every second polyhedron within the columns of face-sharing K6 octahedra is statistically occupied by a sulfide ion. Both of the two different K positions exhibit a sixfold coordination by sulfide anions, with K–S distances between 307.1 and 382.1 pm. In the two title compounds, each of the [InQ4] tetrahedra is overall enclosed by 18 potassium cations. The crystal chemistry of the new indates is discussed and compared with that of the (yet comparatively low number) of alkali chalcogenido metallates(III) of Fe, Al and Ga containing isolated metallate tetrahedra.  相似文献   

11.
Three new thiogermanates (enH)4Ge2S6 (1) and [M(en)3]2Ge2S6 (M=Mn (2), Ni (3); en=ethylenediamine) were synthesized using GeO2 and S8 as starting materials in molar ratio of 1:0.5 under solvothermal conditions. These compounds suggest that the dimeric [Ge2S6]4− anion is likely to be the main germanium-containing species in en system and it also might be preferred as counter anions by the transition metal complex cations in crystallization. The cations of [Mn(en)3]2+ and [Ni(en)3]2+ are even better mineralizers than the protonated amine of [enH]+. The crystal systems of [Ge2S6]4− compounds are related to entities of cations and intermolecular reactions between cations and [Ge2S6]4− anions. The compounds remove ethylenediamine and H2S molecules in multi steps when being heated under nitrogen stream.  相似文献   

12.
The title compound [XylIm2][Cd(SeCN)4] [XylIm2 = p‐bis(N‐methylimidazolyl)xylylene] comprises discrete p‐bis(N‐methylimidazolyl)xylylene cations and [Cd(SeCN)4]2? anions in which the cadmium atoms are tetrahedrally coordinated by four selenium atoms. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

13.
Systematic studies on quaternary thio‐ and selenoborates containing heavier alkaline earth metal cations led to the two new isotypic crystalline phases Sr4.2Ba2.8(BS3)4S and Ba7(BSe3)4Se. Both compounds consist of trigonal‐planar BQ3 (Q = S, Se) units, isolated Q2– anions and the corresponding counter‐ions. The two new chalcogenoborates were prepared in solid state reactions from the metal sulfides (selenides), amorphous boron and sulfur (selenium). Evacuated carbon coated silica tubes were used as reaction vessels since temperatures up to 870 K were applied. Sr4.2Ba2.8(BS3)4S and Ba7(BSe3)4Se crystallize in the monoclinic space group C2/c (no. 15) with a = 9.902(3) Å, b = 23.504(9) Å, c = 9.884(3) Å, β = 90.01(3)° and Z = 4 in the case of the thioborate, while for the selenoborate the lattice parameters a = 10.513(2) Å, b = 25.021(5) Å, c = 10.513(2) Å, β = 90.10(3)° were determined. X‐ray powder patterns are compared to calculated diffraction data obtained from single crystal X‐ray structure determination.  相似文献   

14.
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 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 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 D3h symmetry, whereas [Ge9Zn]2?acts as an electron acceptor when interacting with the triangular face of a D3h‐symmetric [Ge9]4? unit.  相似文献   

15.
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}3PRRI] (R=tBu, RI=(CH2)3CH=CH2; 2 ) and [Ge9{Si(TMS)3}2PRRI] (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)3CH=CH2}PCl ( 1 ) with silylated [Ge9] clusters. Furthermore, the reactivity of the cluster anions 3 a to 11 a towards NHCDippMCl (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 1J(31P-107Ag/109Ag) spin-spin coupling.  相似文献   

16.
La3OCl[AsO3]2: A Lanthanum Oxide Chloride Oxoarsenate(III) with a “Lone‐Pair” Channel Structure La3OCl[AsO3]2 was prepared by the solid‐state reaction between La2O3 and As2O3 using LaCl3 and CsCl as fluxing agents in evacuated silica ampoules at 850 °C. The colourless crystals with pillar‐shaped habit crystallize tetragonally (a = 1299.96(9), c = 558.37(5) pm, c/a = 0.430) in the space group P42/mnm (no. 136) with four formula units per unit cell. The crystal structure contains two crystallographically different La3+ cations. (La1)3+ is coordinated by six oxygen atoms and two chloride anions in the shape of a bicapped trigonal prism (CN = 8), whereas (La2)3+ carries eight oxygen atoms and one Cl? anion arranged in the shape of tricapped trigonal prism (CN = 9). The isolated pyramidal [AsO3]3? anions (d(As–O) = 175–179 pm) consist of three oxygen atoms (O2 and two O3), which surround the As3+ cations together with the free, non‐binding electron pair (lone pair) Ψ1‐tetrahedrally (?(O–As–O) = 95°, 3×). One of the three crystallographically independent oxygen atoms (O1), however, is exclusively coordinated by four (La2)3+ cations in the shape of a real tetrahedron (d(O–La) = 236 pm, 4×). These [(O1)(La2)4]10+ tetrahedra form endless chains in the direction of the c axis through trans‐edge condensation. Empty channels, constituted by the lonepair electrons of the Cl? anions and the As3+ cations in the Ψ1‐tetrahedral oxoarsenate(III) anions [AsO3]3?, run parallel to [001] as well.  相似文献   

17.
Na12Ge17 is prepared from the elements at 1025 K in sealed niobium ampoules. The crystal structure reinvestigation reveals a doubling of the unit cell (space group:P21/c; a = 22.117(3)Å, b = 12.803(3)Å, c = 41.557(6)Å, β = 91.31(2)°, Z = 16; Pearson code: mP464), furthermore, weak superstructure reflections indicate an even larger C‐centred monoclinic cell. The characteristic structural units are the isolated cluster anions [Ge9]4— and [Ge4]4— in ratio 1:2, respectively. The crystal structure represents a hierarchical cluster replacement structure of the hexagonal Laves phase MgZn2 in which the Mg and Zn atoms are replaced by the Ge9 and Ge4 units, respectively. The Raman spectrum of Na12Ge17 exhibits the characteristic breathing modes of the constituent cluster anions at ν = 274 cm—1 ([Ge9]4—) and ν = 222 cm—1 ([Ge4]4—) which may be used for identification of these clusters in solid phases and in solutions. Raman spectra further prove that Na12Ge17 is partial soluble both in ethylenediamine and liquid ammonia. The solution and the solid extract contain solely [Ge9]4—. The remaining insoluble residue is Na4Ge4. By heating the solvate Na4Ge9(NH3)n releases NH3 and decomposes irreversibly at 742 K, yielding Na12Ge17 and Ge.  相似文献   

18.
A convenient method to isolate inverted cucurbit[7]uril (iQ[7]) from a mixture of water‐soluble Q[n]s was established by eluting the soluble mixture of Q[n]s on a Dowex (H+ form) column so that iQ[7] could be selected as a ligand for coordination and supramolecular assembly with alkaline earth cations (AE2+) in aqueous HCl solutions in the presence of [ZnCl4]2? and [CdCl4]2? anions as structure‐directing agents. Single‐crystal X‐ray diffraction analysis revealed that both iQ[7]–AE2+–[ZnCl4]2?–HCl and iQ[7]–AE2+–[CdCl4]2?–HCl interaction systems yielded supramolecular assemblies, in which the [ZnCl4]2? and [CdCl4]2? anions presented a honeycomb effect, and this resulted in the formation of linear iQ[7]/AE2+ coordination polymers through outer‐surface interactions of Q[n]s.  相似文献   

19.
Na6Sn4Se11 · 22 H2O can be crystallised at –8 °C as yellow‐orange needles from the 1 : 2 H2O/CH3OH mother liquor of a superheated reaction mixture of NaOH(s), Sn and Se. The bicyclic [Sn4Se11]6– anion exhibits crystallographic C2 symmetry and is composed of corner‐bridged SnSe4 tetrahedra. Two opposite tin atoms of an Sn4Se4 8‐membered ring are linked by a common Se atom, thereby affording two 6‐membered boat‐shaped Sn3Se3 rings with a shared Sn–Se–Sn bridging unit. [Sn4Se11]6– thus represents the immediate precursor of the well‐known adamantane‐like [Sn4Se10]4– anion.  相似文献   

20.
The structure of the compound [Pt(NH3)4][PtI4] was studied by X‐ray diffractometry at 293 K (r. t.) and at 173 K. The structure is isotypic with that of Magnus' green salt and is unchanged at low temperature except for a slight contraction of the unit cell [tetragonal, P4/mnc; a = b = 9.8024(10) and c = 6.9311(10)Å at r. t; a = b = 9.764(3), c = 6.875(3)Å at 173 K]. It consists of [Pt(NH3)4]2+ cations and [PtI4]2? anions in which the platinum atoms are tetracoordinated by four ammine N or four I atoms in square‐planar arrangements. At 173 K the intramolecular bond lengths are hardly modified, but the intermolecular stacking interaction Pt‐Pt is slightly shortened.  相似文献   

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