Structure of the Ligated Ag60 Nanoparticle [{Cl@Ag12}@Ag48(dppm)12] (where dppm=bis(diphenylphosphino)methane)

A novel bisphosphine ligated Ag₆₀ nanocluster, [{Cl@Ag₁₂}@Ag₄₈(dppm)₁₂], has been dis-covered and characterized by X-ray crystallography. It consists of a central chloride located inside an icosahedral silver core layer, which is further encased by a second shell of 48 silver atoms/ions, which are capped with 12 bis(diphenylphosphino)methane (dppm) ligands. Due to lack of sufficient material the cluster could not be further characterized by other methods. DFT calculations were carried out on the cation [{Cl@Ag₁₂}@Ag₄₈(dppm)₁₂]⁺ to determine if it corresponds to a superatom with a core count of n=58. The DFT optimized structure is in agreement with X-ray ndings, but the low value of the HOMO-LUMO gap does not support superatom stability.     

Synthesis and structure of a water-soluble hexanuclear silver(I) nicotinate cluster comprised of a "cyclohexane-chair"-type of framework, showing effective antibacterial and antifungal activities: use of "sparse matrix" techniques for growing crystals of water-soluble inorganic complexes

The synthesis of a water-soluble anionic silver 2-mercaptonicotinate complex having effective antibacterial and antifungal properties is described. Its structure has been confirmed to be a hexameric cluster by an X-ray diffraction analysis of a mixed Na(+)/Tris(+) salt (Tris(+) = tris(hydroxymethyl)methylammonium cation). The [Ag(mna)](6)(6-) cluster has a Ag(6)S(6) core and an overall shape of twisted hexagonal cylinder with six sulfur atoms and six silver atoms alternating on a puckered drum-like surface. Each Ag atom is trigonally coordinated by one N and two S ligands. The overall [Ag(mna)](6)(6-).4Na(+).2[(HOCH(2))(3)CNH(3)](+).10H(2)O complex has a layered appearance in the crystal packing diagram, with a [Ag(mna)](6)(-) cluster layer alternating with a solvent layer consisting of sodium atoms, Tris buffer cations, and water molecules. The structure is almost identical to that of a neutral [Ag(Hmna)](6) complex reported earlier. The neutral and charged complexes are both known to possess antimicrobial activities, and some biological properties of these and related compounds are briefly discussed in this paper.     

One-dimensional coordination polymers incorporating silver(I) perfluorocarboxylate cuboctahedral clusters and the bis(methylthio)methane ligand

Two topologically comparable complexes, [Ag6(CF3CO2)3(L1-Me)3(SCH3)3]infinity (1) and [Ag6(CF3CF2CO2)3(L1-Me)2(SCH3)3(H2O)]infinity (2), were prepared and characterized by single-crystal diffractometry. The structures consist of Ag12S6 clusters linked by bis(methylthio)methane ligands, L1-Me, thus forming 1D coordination polymers. The 12 Ag atoms of the cluster are situated at the corners of a distorted cuboctahedron. The sulfur atoms of the six mu4-SCH3 entities occupy a position approximately 0.8 A above the center of each of the square faces of the polyhedron. The cleavage of the C-S bond of some of the ligands occurs during the syntheses, producing the -SCH3 anions. The coordination of the silver atoms varies from 5 to 7. The Ag...Ag contacts range from 2.9250(5) to 3.3615(6) A and from 2.961(1) to 3.380(1) A for 1 and 2, respectively. A polymeric ribbon is obtained when four ligands link a given cluster to two others. The chains of 1, held only by van der Waals forces, pack in a hexagonal manner. The two water molecules in 2 (Ag-OH2 = 2.385(7) A) are coordinated to silver atoms of the cluster. They are also strongly hydrogen bonded to the oxygen atoms of two pentafluoropropionate groups, one within the cluster (O...O = 2.741(1) A), the other in an adjacent chain (O...O = 2.818(1) A). The chains, thus H bonded to one another, generate a 2D coordination network.     

以苯硒酚为配体的四核银族合物[Me2N]2[Ag4（SePh）6]·CH3OH的合成与晶体结构

合成了以苯硒酚为配体的四核银族合物[Me2N]2[Ag4(SePh)6]·CH3OH,并用X射线单晶衍射法测定了其晶体结构。簇阴离子的核心Ag4Se6是由4个Ag原子组成的四面体内接于6个Se原子组成的变形八面体中,形成了类金刚烷型结构。     

Synthesis and Crystal Structure of Ag2（admtrz）2（CF3CO2）2（admtrz=4—amino—3,5—dimethyl—1,2,4—triazole）

1 INTRODUCTION Transition metal complexes bridged by 1, 2, 4-triazole group can produce interesting structures and specific properties[1]. Many attempts have been made to synthesize a variety of complexes with paramagnetic centers by using such ligands, and their structures and magnetic properties have been characterized[2]. However, the polynuclear Ag(I) complexes bridged by 1, 2, 4-triazole have been poorly studied[3]. Recently, we have prepared a series of silver(I) triazole complex…     

Linker Flexibility-Dependent Cluster Transformations and Cluster-Controlled Luminescence in Isostructural Silver Cluster-Assembled Materials (SCAMs)

Silver chalcogenolate clusters (SCCs) and silver cluster-assembled materials (SCAMs) are an important category of novel luminescent materials, the emission of which can be modulated by variation of the cluster nodes and linker species. Here, the successfully synthesis of two isostructural 2D SCAMs is reported: Ag₁₂bpa and Ag₁₂bpe are formed by using two linkers with different conformational freedom (bpa=1,2-bis(4-pyridyl)ethane, bpe=1,2-bis(4-pyridyl)ethylene), with dodenuclear silver chalcogenolate clusters as secondary building units (SBUs). Interestingly, nonluminescent Ag₁₂bpa at room temperature could quickly transform into 1D Ag₁₀bpa , with concomitant dissociation of two silver atoms and the remaining ten silver atoms rearranging in the cluster, thus exhibiting an intense yellow phosphorescence after being triggered by acetonitrile (CH₃CN). Similarly, stimulating Ag₁₂bpe with CH₃CN, by contrast, gave another 2D structure Ag₁₂bpe-1b with the distorted SBUs and different topology structure, and both of them are merely red-emissive at low temperature. To note, after exchanging ligands, room-temperature nonluminescent 2D Ag₁₂bpe-1b can be transformed into intensely luminescent 1D Ag₁₀bpa . This linker-flexibility-dependent structural transformation and cluster-based SBU controlled luminescence remains scarce. Our work provides new insights into structure–luminescence relationship in clustered metal–organic frameworks and intelligent stimulus-responsive luminescent materials.     

Synthesis and structure of Ag(1-Me-12-SiPh3-CB11F10): selective F12 substitution in 1-Me-CB11F11- and the first Ag(arene)4+ tetrahedron

The selective substitution of the antipodal F atom in 1-Me-CB(11)F(11)- with a SiPh(3) moiety led to the isolation and structure determination of the cesium(I) and silver(I) salts of the 1-Me-12-SiPh(3)-CB(11)F(10)- anion. The silver salt contains both a nearly trigonal-planar Ag(arene)(3)+ cation and the first example of a Ag(arene)(4)+ cation.     

New halide-centered discrete Ag(I)(8) cubic clusters containing diselenophosphate ligands, [Ag(8)(X)[Se(2)P(OR)(2)](6)](PF(6)) (X = Cl, Br; R = Et, Pr, (i)Pr): syntheses, structures, and DFT calculations

Six clusters Ag(8)(micro(8)-X)[Se(2)P(OR)(2)](6)(PF(6)) (R = Et, X = Cl, 1a, X = Br, 1b; R = Pr, X = Cl, 2a, X = Br, 2b; R = (i)Pr, X = Cl, 3a, X = Br, 3b) were isolated from the reaction of [Ag(CH(3)CN)(4)](PF(6)), NH(4)[Se(2)P(OR)(2)], and Bu(4)NX in a molar ratio of 4:3:1 in CH(2)X(2). Positive FAB mass spectra show m/z peaks at 2573.2 for 1a, 2617.3 for 1b, 2740.9 for 2a, 2786.9 for 2b, 2742.3 for 3a, and 2787.0 for 3b due to respective molecular cation, (M - PF(6))(+). (31)P NMR spectra of 1a-3b display a singlet at delta 82.3, 81.5, 82.9, 81.7, 76.3, and 75.8 ppm with a set of satellites (J(PSe) = 661, 664, 652, 652, 656, and 656 Hz, respectively). The X-ray structure (1a-2b) consists of a discrete cationic cluster in which eight silver ions are linked by six diselenophosphate ligands and a central micro(8)-Cl or micro(8)-Br ion with a noncoordinating PF(6)(-) anion. The shape of the molecule is a halide-centered distorted Ag(8) cubic cluster. The dsep ligand exhibits a tetrametallic tetraconnective (micro(2), micro(2)) coordination pattern, and each caps on a square face of the cube. Each silver atom of the cube is coordinated by three selenium atoms and the central chloride or bromide ion. Additionally, molecular orbital calculations at the B3LYP level of the density functional theory have been carried out to study the Ag-micro(8)-X (X = Cl, Br) interactions for cluster cations [Ag(8)(micro(8)-X)[Se(2)P(OR)(2)](6)](+). Calculations show very weak bonding interactions exist between micro(8)-X and Ag atoms of the cube.     

Hydrothermal Synthesis and X-ray Characterization of Silver(I) Complex:Diacetylthiocarbamide Silver(I) Nitrate,[Ag(CH3CONHC(S)NH2)2](NO3)

1 INTRODUCTION As a thiolate ligand with potential S and N donors, thiourea is interesting due to its multifunctional coor-diation modes (unidentate-N, unidentate-S or biden- tate-N, S)[1]. As a good extracting agent for nobelme-tals[2], thiourea has…     

十二硼十二氢镍乙二胺晶体结构的研究

Ni(en)_3B_(12)H_(12)晶体属于三方晶系,空间群为R_3,晶胞参数为:a=b=12.890(2),c=23.955(20),α=B=90°,Υ=120°,Z=6。在室温下用CAD-4衍射仪收集单晶衍射强度数据(MOK_α);重原子法和差Fourier法解出全部非氢原子坐标,用加氢程序定出全部氢原子的坐标。各原子坐标及热振动参数经全矩阵最小二乘方修正,对于985个独立衍射点[I≥3σ(I)]最后偏离因子R=0.069。结构分析表明,该化合物属于离子型,Ni(en)_-~(2+)离子和B_(12)H_(12)~(-2)离子间相互以正三角双锥方式配位。Ni(en)~(2+)离子具有D_3对称性,Ni-N平均键长为2.138,B_(12)H_(120~(-2)离子呈正二十面体构型,B-B平均键长为1.786。     

Na5[MB24O34(OH)12].nH2O (M = Cr(3+), Al(3+)): unprecedented spherelike polyborate clusters from boric acid flux synthesis

Two novel isotypic polyborate cluster compounds Na 5[MB 24O 34(OH) 12]. nH 2O (M = Cr (3+), Al (3+)) have been synthesized in a boric acid flux closed system at 220 degrees C by using gel as precursors. The structure of the Cr compound was determined by low-temperature single-crystal X-ray diffraction, and the Al compound was confirmed to be isostructural by powder X-ray diffraction and similar FT-IR spectra and thermal behavior. Na 5[CrB 24O 34(OH) 12]. nH 2O crystallizes in the monoclinic space group P2 1/ c with the cell parameters a = 17.4549(3) A, b = 11.1976(2) A, c = 21.2403(3) A, beta = 94.644(2) degrees , V = 4137.85(12) A (3), and Z = 4. The predominant feature of the structure are the spherelike polyborate clusters [MB 24O 34(OH) 12] (5-). The M (3+) cation is located at the center of the cluster, around which four hexaborate units ([B 6O 10(OH) 3] (5-)) are tetrahedrally assembled in almost a perfect T d symmetry. To the best of our knowledge, [MB 24O 34(OH) 12] (5-) is the first example of a polyborate cluster that contains 24 boron atoms. Upon heating, the compounds show two steps of weight loss, including the loss of the disengaged water and dehydration of the hydroxy groups. The first step is reversible, retaining the structure framework. The second weight loss is continuous and irreversible.     

[Ag12F(NPEt3)8]3+: Ein durch Fluorid gefüllter Metalla‐Cryptand

[Ag₁₂F(NPEt₃)₈]³⁺: A Metalla‐Cryptand filled with a Fluoride Ion [Ag₁₂F(NPEt₃)₈](SiF₆)_1,5 ( 1 ) was obtained from the reaction of silver(I) fluoride with the silylated phosphaneimine Me₃SiNPEt₃ in acetonitrile. It forms colorless, light‐ and hydrolysis‐sensitive crystals, which incorporate acetonitrile that is lost in vacuo. 1 · 2,4 CH₃CN was characterized by its IR spectrum and by X‐ray crystal structure analysis. Space group Pa 3, Z = 8, a = 2734.8(1) pm at 153 K, R = 0.059. The compound consists of cations [Ag₁₂F(NPEt₃)₈]³⁺ (point group C₃), SiF₆^2– counter‐ions and acetonitrile molecules which show no interactions. In the cation the silver atoms are located on the edges of a nearly undistorted cube and the N atoms of the phosphoraneiminato groups (NPEt₃^–) occupy the vertices. A fluoride ion in the center of the cube has contacts of nearly similar length to the 12 silver atoms (mean distance 304.7 pm).     

CRYSTAL STRUCTURE OF BIS(TETRAETHYLAMMONIUM) BIS-[BIS(p-CHLOROPHEN- THIOLATO)(μ-SULFIDO) IRON(Ⅲ)], (Et4N)_2[Fe_2S_2(SC_6H_4Cl-p)_4]

<正> (Et_4N)_2[Fe_2S_2(SC_6H_4Cl-p)_4], Mr=939.89, F(000)=492, triclinic, P1,a=9.358(4), b=10.535(3), c=14.537(2)A,α=64.96(2),β=70.29(2),γ= 68.22(2)°, V=1177.8(13)A3, Z=1,Dc=1.325 gcm-3, MoKα ,λ=0.71069A. Final R= 0.061,Rw=0.076, for 1794 independent observed reflections. The anion contains a planar Fe2S2 core. Each iron atom is coordinated by two μ2-S atoms and two thiolate sulfur atoms to form the tetrahedral geometry. The structure of the cation has its positional disorder.     

Coordination of a chiral tin(ii) cation bearing a bis(oxazoline) ligand with tetrahydrofuran derivatives

The reaction of SnCl(2) with the lithio derivative of a bis(oxazoline) ligand precursor afforded the enantiomeric chlorostannylene whose chloride ion can be substituted by several neutral or anionic Lewis donors. Abstraction of the chloride ion from the chlorostannylene with silver salts gave the corresponding tetrahydrofuran (THF) complexes of a chiral tin(ii) cation in 1,2-dimethoxyethane (DME) containing THF. That is, the reaction with silver hexafluoroantimonate (AgSbF(6)) afforded the THF complex without interaction with the counteranion. In contrast, reaction with silver triflate (AgOTf) gave the THF complex whose tin center had a pseudo-trigonal bipyramidal structure with two nitrogen atoms of a bidentate ligand and a lone pair at the equatorial positions and one of the oxygen atoms of triflate and an oxygen atom of THF at the apical positions in the solid state. Use of 3-methyltetrahydrofuran (3-MeTHF) instead of THF afforded the 3-MeTHF complexes, where the R-enantiomer of 3-MeTHF predominantly coordinates to the tin center. The previously reported germanium(ii) analogue of the tin(ii) cation indicated a similar enantioselectivity for the coordination of 3-MeTHF on the germanium center.     

杂-双核配合物[CaCu(C3H2O4)2(H2O)4]n的合成、晶体结构及热稳定性

The title complex, [CaCu(C3H2O4)2(H2O)4]n, with a formula of C6H12CaCuO12 and Mr=379.78 has been sy-nthesized and characterized by single crystal X-ray diffraction structure analysis, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is Orthorhombic, space group Pbcn with a=0.669 21(5) nm, b=1.370 23(5) nm, c=1.322 39(10) nm, V=1.212 59(16) nm3, Dc=2.080 g·cm-3, μ=2.288 mm-1, F(000)=772 and Z=4. The final R=0.054 0 and wR=0.112 8 for 1 189 observed reflections with I>2σ(I). The structure of the title complex consists of CaO8 polyhedra and CuO6 elongated octahedra linked together by malonate ligands. The Ca(Ⅱ) cation, on a twofold axis, is coordinated by two water molecules and six malonate O atoms. The Cu(Ⅱ) cation, which lies in a centre of symmetry in an octahedral arrangement, is coordinated by four malonate O atoms and two water molecules. The structure comprises alternating layers along the [101] plane, with the shortest Cu…Cu distance of 0.762 46(6) nm. The whole 3D structure is maintained and stabilized by the presence of hydrogen bonds. Its thermo gravimetric analysis was determined by TG-DTG techniques. CCDC:663184.     

双核银络合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成与结构

二-(二苯基膦)甲烷(dppm)是一种易与金属形成多核络合物的有机膦配体。我们用dppm作为配体合成了一系列银的多核络合物,并对其结构进行了研究。本文报导了其中一个双核化合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成及晶体结构、分子结构的测定。     

夹心三明治结构的二十五核银硫簇合物[Ag25(SC6H4Pri)18 (dppp)6](CF3SO3)7·CH3CN：结构表征及光学性能

在本研究中,使用(ⁱPrC₆H₄SAg)_n作为合成银硫纳米簇合物的前驱体。当存在辅助的双膦配体1, 3-双(二苯基膦)丙烷(dppp)及可溶性银盐(CF₃SO₃Ag),在超声合成条件下,获得了一例二十五核银硫簇合物Ag₂₅,并借助X射线单晶衍射技术确定相应的分子结构。该银硫簇合物具有夹心三明治的骨架结构：分别由两个结构相似的圆柱体共享一个七核纯银簇所构成的金属簇平面。固态紫外可见漫反射光谱测试表明该簇合物的能级带隙为2.5 eV,属于半导体材料的范畴。固态发光测试显示,该簇合物在室温下发射绿光。     

Gas-phase interaction of thiophene with the Ti(8)C(12)(+) and Ti(8)C(12) met-car clusters

The reactivity of the Ti(8)C(12)(+) met-car cation toward thiophene was investigated using density functional theory (DFT) and mass selective ion chemistry. It is shown that the experimentally observed mass spectrum can be well described by the DFT calculations. In contrast to the weak bonding interactions seen for thiophene on a TiC(001) surface, the Ti(8)C(12)(+) met-car cation is able to interact strongly with up to four thiophene molecules with the cluster staying intact. In the most stable conformation, the thiophene molecules bond to the four low-coordinated Ti(0) sites of Ti(8)C(12)(+) via a eta(5)-C,S coordination. The stability and the activity of the Ti(8)C(12)(+) met-car is observed to increase with an increasing number of attached thiophene molecules at the Ti(0) sites, which is associated with a significant transfer of electron density from thiophene to the cluster. The additional electron density on the Ti(8)C(12)(+) cation cluster, however, is not sufficient to cleave the C-S bonds of thiophene and the dissociation reaction of thiophene is predicted to be a highly activated process. By contrast, DFT calculations for the neutral Ti(8)C(12) met-car predict that the dissociation reaction leading to adsorbed S and C(4)H(4) fragments is energetically favorable for the first thiophene molecule. The binding behavior for subsequent addition of thiophene molecules to the neutral met-car is also presented and compared to that of the cation.     

CsR(R(6)CoI(12))2 (R = Gd, Er) and (CeI)0.26(Ce(6)MnI(9))2: two new structure types featuring R(6)Z clusters

Compounds adopting two new structure types containing discrete lanthanide clusters have been found, CsR(R6CoI12)2 (R = Gd or Er) and (CeI)0.26(Ce6MnI9)2. CsEr(Er6CoI12)2 and CsGd(Gd6CoI12)2 were synthesized in reactions of CsI, RI3, CoI2, and R metals (3:19:6:23) heated to 750 degrees C for 500 h followed by slow cooling (0.1 degrees C/min). The X-ray crystal structure of CsEr(Er6CoI12)2 was solved in the Pa3 space group with a = 18.063(2) A at 250 K (Z = 4, R1 [I > 2sigma(I)] = 0.0459). (CeI)0.26(Ce6MnI9) was synthesized by combining KI, CeI3, MnI2, and Ce metal and heating to 850 degrees C for 500 h. The single-crystal X-ray structure for (CeI)0.26(Ce6MnI9)2 was solved in the trigonal, P3 (147) space group with lattice parameters of a = 11.695(1) A and c = 10.8591(2) A (Z = 2, R1 [I > 2sigma(I)] = 0.0895). Elemental analyses (X-ray photoelectron spectroscopy (XPS) and atomic absorption spectroscopy (AAS)) were performed and show the absence of potassium in the structure. A disorder model was refined for the atoms in the large cavity. The magnetic susceptibility data for CsGd(Gd6CoI12)2 is consistent with strong intracluster ferromagnetic coupling, but intercluster antiferromagnetic coupling suppresses the susceptibility below 70 K.     

Synthesis of stable crystals of a self-assembled centered icosahedral samarium cluster formed by bis(L-prolinato)nickel(II) ligands

A centered icosahedral 12-coordinate samarium cluster formed by six bis(L-prolinato)nickel(II) ([Ni(pro)2]) ligands, [Sm(Ni(pro)2)6]3+, was prepared. The reaction of Sm with [Ni(pro)2] in a small excess (a 2-fold excess) and also in a large excess (even a 10-fold excess) of the latter produced the cluster. Therefore, this system is a self-assembly. In the cluster, each nickel atom is surrounded by six atoms: two amino nitrogens, two carboxylate oxygens which form chelate rings with the nitrogen atoms, and two carboxylate oxygen atoms which link the neighboring nickel atoms. The samarium atom is coordinated by six [Ni(pro)2] ligands, and the metal is in an icosahedral environment formed by 12 oxygen atoms. The icosahedral geometry is almost ideal. Crystals of [Sm(Ni(pro)2)6](ClO4)3.6MeOH, which were prepared from a methanol solution, immediately decompose after filtration because of loosely trapped MeOH molecules in the crystal lattice. Therefore, crystals without MeOH molecules, which must be stable, were prepared by recrystallization from acetonitrile with tetramethylammonium perchlorate (TMAP). According to the X-ray crystal analysis, the cluster is TMA[Sm(Ni(pro)2)6](ClO4)4, cubic of space group F23, with a = 21.273(9) A, V = 9626(1) A3, and Z = 4; R = 0.053 (Rw = 0.049) for 1296 reflections. In addition, several crystals of cluster salts that have different counteranions, i.e., tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), iodide (I-), and nitrate (NO3-), were prepared. The order of increasing ease of crystallization of the cluster salts was I- > PF6- approximately ClO4- > BF4- > NO3-. The cluster structure is retained in alcohol and acetonitrile solutions; the UV-vis spectra of the solutions are perfectly consistent with the powder diffuse reflection spectrum. Cyclic voltammograms of [Sm(Ni(pro)2)6]3+ in acetonitrile proved that the structure of [Sm(Ni(pro)2)6]3+ is retained in the redox process and that the nickel atoms electrochemically interact with one another. Thermal analysis of the cluster salts with different counteranions was investigated. The results imply that the cluster is very stable until bis(L-prolinato)nickel(II) ligands, which form the cage structure, disintegrate and that the thermal decomposition processes of the cluster salts depend on their counteranions.