1D helix, 2D brick-wall and herringbone, and 3D interpenetration d10 metal-organic framework structures assembled from pyridine-2,6-dicarboxylic acid N-oxide

Five novel interesting d(10) metal coordination polymers, [Zn(PDCO)(H2O)2]n (PDCO = pyridine-2,6-dicarboxylic acid N-oxide) (1), [Zn2(PDCO)2(4,4'-bpy)2(H2O)2.3H2O]n (bpy = bipyridine) (2), [Zn(PDCO)(bix)]n (bix = 1,4-bis(imidazol-1-ylmethyl)benzene) (3), [Zn(PDCO)(bbi).0.5H2O]n (bbi = 1,1'-(1,4-butanediyl)bis(imidazole)) (4), and [Cd(PDCO)(bix)(1.5).1.5H2O]n (5), have been synthesized under hydrothermal conditions and structurally characterized. Polymer 1 possesses a one-dimensional (1D) helical chainlike structure with 4(1) helices running along the c-axis with a pitch of 10.090 Angstroms. Polymer 2 has an infinite chiral two-dimensional (2D) brick-wall-like layer structure in the ac plane built from achiral components, while both 3 and 4 exhibit an infinite 2D herringbone architecture, respectively extended in the ac and ab plane. Polymer 5 features a most remarkable and unique three-dimensional (3D) porous framework with 2-fold interpenetration related by symmetry, which contains channels in the b and c directions, both distributed in a rectangular grid fashion. Compounds 1-5, with systematic variation in dimensionality from 1D to 2D to 3D, are the first examples of d(10) metal coordination polymers into which pyridinedicarboxylic acid N-oxide has been introduced. In addition, polymers 1, 4, and 5 display strong blue fluorescent emissions in the solid state. Polymer 3 exhibits a strong SHG response, estimated to be approximately 0.9 times that of urea.     

Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes

The addition of an excess of phenyldiazomethane to chlorobenzene solutions of the cationic dinitrosyl bisphosphine rhenium(-I) complexes [Re(NO)2(PR3)2][BAr(F)4] (R = Cy 1a, R = (i)Pr 1b) gave the corresponding benzylidene complexes [Re{=CH(C6H5)}(NO)2(PR3)2][BAr(F)4] (2a and 2b) in good yields. The treatment of 2b with dioxygen resulted in the oxidation of one of the nitrosyl ligands into the corresponding eta2-nitrito (3b) and nitrato complexes (4b) both in the solid state and in solution. In the case of the tricyclohexylphosphine derivative 2a the analogous conversion was not observed. A mechanism for the reaction of 2b with O2 is proposed which is based on an initial SET to the O2 molecule and subsequent formation of a peroxynitrite complex followed by the formation of a dinuclear mU-N2O4 intermediate. This in turn would undergo fission of the peroxo bond to afford 3b. A related sequence of steps is anticipated for the transformation of 3b to 4b. Furthermore, a similar mechanism seems reasonable for the seemingly topochemical reaction of 2b to 3b and 4b in the solid state. The initial SET to dioxygen and subsequent formation of the peroxynitrite complex is supported by DFT calculations on the trimethylphosphine model complexes [Re=CH{C6H5})(NO)2(PMe3)2]n+ (n = 1 and 2).     

Synthesis, characterisation and molecular structure of Re(III) 2-oxacyclocarbenes stabilised by a benzoyldiazenido ligand

A family of new Fischer-type rhenium(III) benzoyldiazenido-2-oxacyclocarbenes of formula [(ReCl2[eta1-N2C(O)Ph][=C(CH2)nCH(R)O](PPh3)2][n = 2, R = H (2), R = Me (3); n = 3, R = H (4), R = Me (5)] have been prepared by reaction of [ReCl2[eta2-N2C(Ph)O](PPh3)2] (1) with omega-alkynols, such as 3-butyn-1-ol, 4-pentyn-1-ol, 4-pentyn-2-ol, 5-hexyn-2-ol in refluxing THF. The correct formulation of the carbene derivatives 2-5 has been unambiguously determined in solution by NMR analysis and confirmed for compounds 2-4 by X-ray diffraction methods in the solid state. All complexes are octahedral with the benzoyldiazenido ligand, Re[N2C(O)Ph], adopting a "single bent" conformation. The coordination basal plane is completed by an oxacyclocarbene ligand and two chlorine atoms. Two triphenylphosphines in trans positions with respect to each other complete the octahedral geometry around rhenium. The reactivity of 1 towards different alkynes and alkenes including propargyl- and allylamine has been also studied. With propargyl amine, monosubstituted or bisubstituted complexes, [(ReCl2[eta1-N2C(O)Ph][eta1-NH2CH2C triple bond CH]n(PPh3)(3-n)][n= 1 (6); n = 2 (7)], have been isolated depending on the reaction conditions. In contrast, the reaction with allylamine gave only the disubstituted complex [(ReCl2[eta1-N2C(O)Ph][eta1-NH2CH2CH=CH2]2(PPh3)] (8). The molecular structure of the monosubstituted adduct has been confirmed by X-ray analysis in the solid state.     

Phenyltin-substituted 9-tungstogermanate and comparison with its tungstosilicate analogue

Reaction of (C 6H 5)SnCl 3 with Na 10[ A-alpha-GeW 9O 34] in water results in the monomeric, trisubstituted Keggin species [{(C 6H 5)Sn(OH)} 3( A-alpha-GeW 9O 34)] (4-) ( 1), constituting the first organotin derivative of a trilacunary Keggin tungstogermanate. Polyanion 1 could be obtained as two different cesium salts depending on the applied isolation strategy: Cs 3Na[{(C 6H 5)Sn(OH)} 3( A-alpha-GeW 9O 34)].9H 2O ( CsNa-1) and Cs 3[{(C 6H 5)Sn(OH)} 3( A-alpha-HGeW 9O 34)].8H 2O ( Cs-H1). The monomeric phenyltin-containing tungstosilicate [{(C 6H 5)Sn(OH)} 3( A-alpha-SiW 9O 34)] (4-) ( 2) and the dimeric, sandwich-type derivative [{(C 6H 5)Sn(OH)} 3( A-alpha-H 3SiW 9O 34) 2] (8-) ( 3) have also been isolated as the cesium salts Cs 3Na[{(C 6H 5)Sn(OH)} 3( A-alpha-SiW 9O 34)].9H 2O ( CsNa-2), Cs 4[{(C 6H 5)Sn(OH)} 3( A-alpha-SiW 9O 34)].13H 2O ( Cs-2), and Cs 8[{(C 6H 5)Sn(OH)} 3( A-alpha-H 3SiW 9O 34) 2].23H 2O ( Cs-3), respectively. We have investigated in detail the similarities and differences in the reactivity of (C 6H 5)Sn (3+) with [ A-alpha-GeW 9O 34] (10-) vs [ A-alpha-SiW 9O 34] (10-). All five compounds have been characterized in the solid state by means of elemental analysis, infrared spectroscopy, thermogravimetry, and single-crystal X-ray diffraction, representing the first structural analysis for polyanions 1- 3. A full solution characterization of 1 by multinuclear NMR spectroscopy ( (1)H, (13)C, (119)Sn, and (183)W) has also been performed. The monomeric polyanions 1 and 2 are closely associated in the solid state through (Sn)O-H...O t (O t: terminal oxygen atom) hydrogen bonds reinforced by weak C-H...O t contacts to form 2-dimensional ( CsNa-1 and CsNa-2) or 1-dimensional ( Cs-H1) arrangements, and also dimeric entities ( Cs-2) depending on the network of intermolecular interactions.     

1D molecular ladder of the ionic complex of terbium-4-sebacoylbis(1-phenyl-3-methyl-5-pyrazolonate) and sodium dibenzo-18-crown-6: synthesis, crystal structure, and photophysical properties

On the basis of the novel heterocyclic beta-diketone, 4-sebacoylbis(1-phenyl-3-methyl-5-pyrazolone (H 2SbBP), three new lanthanide complexes Tb 2(SbBP) 3(H 2O) 2 ( 1), Gd 2(SbBP) 3(H 2O) 2 ( 2), and [Tb(SbBP) 2] [Na(DB18C6)H 2O] ( 3) have been synthesized and characterized by various spectroscopic techniques. The single-crystal X-ray diffraction analysis of 3 reveals that the complex crystallizes in the monoclinic space group C2/ c with a = 25.300(6) A, b = 19.204(7) A, c = 15.391(3) A, beta = 93.17(3) degrees , and V = 7466(4) A (3). The crystal structure of 3 is heterodinuclear and features a Tb (3+) center surrounded by two tetradentate bispyrazolone ligands in a somewhat distorted square-antiprismatic geometry. The Na (+) coordination environment is distorted hexagonal pyramidal and involves six oxygen atoms furnished by DB18C6 and one oxygen atom from a water molecule. The X-ray diffraction study of 3 also revealed an interesting 1D molecular ladder structure based on C-H/pi, intra- and intermolecular hydrogen-bonding interactions. The photophysical properties of 1 and 3 in solid state have been investigated, and the quantum yields and (5)D 4 lifetimes were found to be 4.82 +/- 0.01% and 18.13 +/- 0.82% and 1.11 +/- 0.01 and 2.82 +/- 0.02 ms, respectively.     

Two one-dimension copper(II) coordination polymers based on imine-based bidentate Schiff-base ligand: synthesis, crystal structure and luminescent properties

Two new one-dimension copper(II) coordination polymers [CuL(2)(NCS)(2)](n) (1) and [CuL(2)(NO(3))(2)](n) (2) (L=(C(5)H(4)N)C(CH(3))=N-N=(CH(3))C(C(5)H(4)N)) have been synthesized and characterized by IR, elemental analysis, TG technique and X-ray crystallography. Each Cu(II) atom has a distorted octahedral N(6) (1) or N(4)O(2) (2) environment with four pyridyl N atoms from four ligands and two N atoms from two NCS(-) anions for polymer 1 or two O atoms from two NO(3)(-) anions for polymer 2, respectively. A pair of bis-monodentate bridging ligands links two Cu(II) centers to form one dimension chain structure containing bimetallic 22-membered macrometallacyclic rings. 1D chain is held together with its neighboring ones via C-H?S hydrogen bonds for 1 and C-H?O hydrogen bonds, C-H?π interactions for 2 to form a 3D supramolecular structure, respectively. The luminescent properties of the polymers 1 and 2 were investigated in the solid state at room temperature.     

Heterodimetallic germanium(IV) complex structures with transition metals

The hydrothermal synthesis and structural characterization of a number of complex compounds containing the divalent tris(oxalato-O,O')germanate anion, [Ge(C2O4)3]2-, or the neutral bis(oxalate-O,O')germanium fragment, [Ge(C2O4)2], with transition-metal (M) cationic complexes of 1,10'-phenanthroline (phen) is reported: [M(phen)3][Ge(C2O4)3].xH2O [where M2+ = Cu2+ (1a and 1b), Fe2+ (2a and 2b), Ni2+ (3), Co2+ (4); x = 0.2 for 2b], [MGe(phen)2(mu2-OH)2(C2O4)2] [where M2+ = Cd2+ (5) and Cu2+ (6)]. The isolation of two polymorphs with Cu2+ (1a and 1b) and other pseudo-polymorphs for Fe2+ (2a and 2b) was rationalized based on slightly different molar ratios for the starting materials. All compounds have been characterized using EDS, SEM, vibrational spectroscopy (FT-IR and FT-Raman), thermogravimetry, and CHN elemental composition and their structure determined on the basis of single-crystal X-ray diffraction studies. The crystal packing of the different chemical moieties for each series of compounds was discussed on the basis of the various intermolecular interactions present (strong C-H...pi and weak C-H...O hydrogen-bonding interactions, C-H...pi and pi-pi contacts).     

Understanding the structural properties of a homologous series of bis-diphenylphosphine oxides

A homologous series of bis-diphenylphosphine oxides (C6H5)2PO(CH2)(n)PO(C6H5)2 (with n = 2-8; denoted 2-8] have been investigated to explore the effects of a range of competing and cooperative intermolecular and intramolecular interactions on the structural properties in the solid state. The important factors influencing the structural properties include intramolecular aspects such as the conformation of the aliphatic chain and the intramolecular interaction between the two P=O dipoles in the molecule, and intermolecular aspects such as long-range electrostatic interactions (dominated by the arrangement of the P=O dipoles), C-H...O interactions, C-H...pi interactions and pi...pi interactions. Compounds 3 and 5 could be crystallized only as solvate co-crystals (3 water and 5 x (toluene)2], whereas the crystal structures of all the other compounds contain only the bis-diphenylphosphine oxide molecule. The crystal structures have been determined from single-crystal X-ray diffraction data, with the exception of 7 (which has been determined here from powder X-ray diffraction data) and 4 (which was known previously). The compounds with even n represent a systematic structural series, exhibiting characteristic, essentially linear P=O...P=O...P=O dipolar arrays, together with C-H...O and C-H...pi interactions. For the compounds with odd n, on the other hand, uniform structural behaviour is not observed across the series, although certain aspects of these crystal structures contribute in a general sense to our understanding of the structural properties of bis-diphenylphosphine oxides. Importantly, for the compounds with odd n, there is "frustration" with regard to the molecular conformation, as the preferred all-anti conformation of the aliphatic chain gives rise to an unfavourable parallel alignment of the two P=O dipoles within the molecule. Clearly the importance of avoiding a parallel alignment of the P=O dipoles becomes greater as n decreases. Local structural aspects (investigated by high-resolution solid-state 31P NMR spectroscopy) and thermal properties of the bis-diphenylphosphine oxide materials are also reported.     

Synthesis and characterization of new coordination polymers generated from oxadiazole-containing organic ligands and inorganic silver(I) salts

The coordination chemistry of the oxadiazole-containing rigid bidentate ligands 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L2) and 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole (L3) with inorganic Ag(I) salts has been investigated. Four new coordination polymers were prepared by solution reactions and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. [[Ag(L2)]SO3CF3]n (1)(triclinic, P1; a = 10.1231(7) A, b = 13.9340-(10) A, c = 13.9284(10) A, alpha = 116.7300(10) degrees, beta = 94.6890(10) degrees, gamma = 108.7540(10) degrees, Z = 4) was obtained by the combination of L2 with AgOTf in a CH2Cl2/CH3OH mixed-solvent system and features a unique one-dimensional elliptical macrocycle-containing chain motif. The approximate dimensions of the rings are ca. 22 x 11 A. [[Ag-(L2)](ClO4)(CH3OH)0.5(H2O)0.5]n (2) (triclinic, P1; a = 8.4894(5) A, b = 13.9092(8) A, c = 14.1596(8) A, alpha = 71.1410(10) degrees, beta = 77.3350(10) degrees, gamma = 81.5370(10) degrees, Z = 4) was generated from the reaction of L2 with AgClO4 in a H2O/CH3OH mixed-solvent system and consists of one-dimensional chains that are linked to each other by weak noncovalent pi-pi interactions into two-dimensional sheets. Uncoordinated ClO4-counterions and guest solvent molecules are located between the layers. [[Ag(L2)]NO3]n (3) was obtained by the combination of L2 with Ag(NO3)2 in a MeOH/H2O mixed-solvent system (triclinic, P1; a = 8.3155(6) A, b = 8.8521(6) A, c = 9.8070(7) A, alpha = 74.8420(10) degrees, beta = 77.2800(10) degrees, gamma = 68.6760(10) degrees, Z = 2). In the solid state, it exhibits an interesting pair of chains associated with C-H...O hydrogen bonds. [[Ag(L3)]SO3CF3]n (4) is generated from L3 and AgSO3CF3 in a CH2Cl2/MeOH mixed-solvent system and crystallizes in the unusual space group Pnnm, with a = 7.9341(4) A, b = 11.5500(5) A, c = 18.1157(8) A, and Z = 4. It adopts a novel three-dimensional structural motif in the solid state with big rhombic channels (ca. 15 x 10 A).     

Toward an intimate understanding of the structural properties and conformational preference of oxoesters and thioesters: gas and crystal structure and conformational analysis of dimethyl monothiocarbonate, CH3OC(O)SCH3

[structure: see text] The molecular structure and conformational properties of dimethyl monothiocarbonate, CH3OC(O)SCH3, have been studied in the gas phase by gas electron diffraction (GED) and vibrational spectroscopy and in the solid state by X-ray crystallography. The experimental investigations were supplemented by quantum chemical calculations at the B3LYP/6-311++G(3df,2p) and MP2/6-311++G(2df,p) levels of approximation. The gaseous molecule exhibits only one conformation having Cs symmetry with synperiplanar orientation of both the C-S and the C-O single bonds relative to the C=O double bond. The following skeletal geometric parameters were derived from the GED analysis (r(hl) values with 3sigma uncertainties): C=O = 1.203(4) A, C(sp(2))-O = 1.335(5) A, C(sp(3))-O = 1.437(5) A, C(sp(2))-S = 1.763(5) A, and C(sp(3))-S = 1.803(5) A; O=C-O = 125.9(8) degrees , O=C-S = 125.7(7) degrees , O-C-S = 108.4(9) degrees , and C-O-C = 113.4(15) degrees . The structure of a single crystal, grown by a miniature zone-melting procedure, was determined by X-ray diffraction analysis at a low temperature. The crystalline solid [monoclinic, P2(1)/n, a = 12.6409(9) A, b = 4.1678(3) A, and c = 19.940(1) A, beta = 98.164(1) degrees ] exists exclusively as molecules in the synperiplanar conformation and with geometrical parameters that agree with those of the molecule in the gas phase. The results are discussed in terms of anomeric and mesomeric effects and in terms of a natural bond orbital analysis.     

对氯苄基三苯基镌-马来二氰基二硫烯镍配合物的合成和晶体结构

合成了一种新的含取代苄基三苯基镌的马来二氰基二硫烯镍配合物[ClBzTPP]2[M（mnt）2]·H2O（[ClBzTPP]’代表对氯苄基三苯基锑阳离子,mnt^2-代表马来二氰基二硫烯阴离子）．配合物为三斜晶系,空间群Pi,晶胞参数为a=1．0585（2）nm,b=1．1089（2）nm,c=1．1570nm,α=81．98（1）°,β=84．95（1）°,γ=84．45（1）°,V=1．3691（4）nm^3,Z=1,最终一致性因子R=0．0584．该配合物由2个[ClBzT—PP]^＋阳离子,1个[M（mnt）2]^2-阴离子和1个H2O组成．其结构特点是配合物中的[C1BzTPP]’阳离子和Ni（mnt）2^2-阴离子沿c轴方向堆积成柱,并通过C—H…S,C—H…π,C—H…Ni氢键和π-π堆积作用形成了二维网状结构．     

两个二维Cd(Ⅱ)配位聚合物的合成、晶体结构和荧光性质

具有d^10电子结构的简单金属配合物是不发光的。然而,采用具有π共轭芳香类有机物为配体所构建的Zn(Ⅱ)和Cd(Ⅱ)配合物,特别是具有重复单元结构的配位超分子和配位聚合物,能够发射较强的荧光,由于它们的配位数和结构的多样性,如[Cd4(betc)2(phen)2(H2O)]n(bete=1,2,4,5-benzenetetracarboxyl),[Cd(isonicotinate)2(EtOH)](EtOH),使这类化合物往往显示出一些新奇的功能。本文分别采用均苯四甲酸根和烟酸根为桥配体,合成了两种具有二维无限结构的Cd(Ⅱ)配位聚合物,它们在紫外光照射下,可以发出较强的蓝色荧光。     

Primary and secondary phosphine complexes of iron porphyrins and ruthenium phthalocyanine: synthesis, structure, and P-H bond functionalization

Reduction of [Fe(III)(Por)Cl] (Por = porphyrinato dianion) with Na2S2O4 followed by reaction with excess PH2Ph, PH2Ad, or PHPh2 afforded [Fe(II)(F20-TPP)(PH2Ph)2] (1a), [Fe(II)(F20-TPP)(PH2Ad)2] (1b), [Fe(II)(F20-TPP)(PHPh2)2] (2a), and [Fe(II)(2,6-Cl2TPP)(PHPh2)2] (2b). Reaction of [Ru(II)(Pc)(DMSO)2] (Pc = phthalocyaninato dianion) with PH2Ph or PHPh2 gave [Ru(II)(Pc)(PH2Ph)2] (3a) and [Ru(II)(Pc)(PHPh2)2] (4). [Ru(II)(Pc)(PH2Ad)2] (3b) and [Ru(II)(Pc)(PH2Bu(t))2] (3c) were isolated by treating a mixture of [Ru(II)(Pc)(DMSO)2] and O=PCl2Ad or PCl2Bu(t) with LiAlH4. Hydrophosphination of CH2=CHR (R = CO2Et, CN) with [Ru(II)(F20-TPP)(PH2Ph)2] or [Ru(II)(F20-TPP)(PHPh2)2] in the presence of (t)BuOK led to the isolation of [Ru(II)(F20-TPP)(P(CH2CH2R)2Ph)2] (R = CO2Et, 5a; CN, 5b) and [Ru(II)(F20-TPP)(P(CH2CH2R)Ph2)2] (R = CO2Et, 6a; CN, 6b). Similar reaction of 3a with CH2=CHCN or MeI gave [Ru(II)(Pc)(P(CH2CH2CN)2Ph)2] (7) or [Ru(II)(Pc)(PMe2Ph)2] (8). The reactions of 4 with CH2=CHR (R = CO2Et, CN, C(O)Me, P(O)(OEt)2, S(O)2Ph), CH2=C(Me)CO2Me, CH(CO2Me)=CHCO2Me, MeI, BnCl, and RBr (R = (n)Bu, CH2=CHCH2, MeC[triple bond]CCH2, HC[triple bond]CCH2) in the presence of (t)BuOK afforded [Ru(II)(Pc)(P(CH2CH2R)Ph2)2] (R = CO2Et, 9a; CN, 9b; C(O)Me, 9c; P(O)(OEt)2, 9d; S(O)2Ph, 9e), [Ru(II)(Pc)(P(CH2CH(Me)CO2Me)Ph2)2] (9f), [Ru(II)(Pc)(P(CH(CO2Me)CH2CO2Me)Ph2)2] (9g), and [Ru(II)(Pc)(PRPh2)2] (R = Me, 10a; Bu(n), 10b; Bn, 10c; CH2CH=CH2, 10d; CH2C[triple bond]CMe, 10e; CH=C=CH2, 10f). X-ray crystal structure determinations revealed Fe-P distances of 2.2597(9) (1a) and 2.309(2) A (2bx 2 CH2Cl2) and Ru-P distances of 2.3707(13) (3b), 2.373(2) (3c), 2.3478(11) (4), and 2.3754(10) A (5b x 2 CH2Cl2). Both the crystal structures of 3b and 4 feature intermolecular C-H...pi interactions, which link the molecules into 3D and 2D networks, respectively.     

Molecular catenation via metal-directed self-assembly and pi-donor/pi-acceptor interactions: efficient one-pot synthesis, characterization, and crystal structures of [3]catenanes based on Pd or Pt dinuclear metallocycles

Dinuclear square metallocycles 3a,b assemble spontaneously when M(en)(OTf)2 (M = Pd, Pt) and a 4,4'-bipyridinium ligand are mixed in acetonitrile. Six new [3]catenanes were prepared in good yields by thermodynamically driven self-assembly reaction of molecular squares 3a,b and pi-complementary dioxoaryl cyclophanes. Single-crystal X-ray analyses of the [3]catenanes revealed the insertion of two aromatic units inside the metallocycle cavity. The structures are stabilized by means of a combination of pi-pi stacking, [C-H...pi] interactions, and [C-H...O] hydrogen bonds. [3]Catenane (DB24C8)2-(3a) showed in solid-state two external DB24C8 rings positioned over the Pd(en) corners, which are held in position by [N-H...O] hydrogen bonds. Furthermore, formation of catenane (DB24C8)2-(3a) can be switched off and on in a controllable manner by successive addition of KPF6 and 18-crown-6.     

Self-complementary

Three [3]catenanes with cavities large enough to accommodate aromatic guests have been designed and synthesized (yields = 5-20 %) by means of kinetically controlled self-assembly processes. The X-ray structural analysis of one of three [3]catenanes confirmed the presence of a rectangular cavity (dimensions = 7 x 11 A) lined by pi-electron-rich recognition sites and hydrogen-bond acceptor groups. In spite of their apparently ideal recognition features, none of these [3]catenanes bind guests incorporating a pi-electron-deficient bipyridinium unit. However, the template-directed syntheses of the [3]catenanes also produce, in yields of 2-23%, [2]catenanes incorporating a 1,5-dioxynaphtho[38]crown-10 interlocked with a bipyridinium-based tetracationic cyclophane. The X-ray structural analyses of two of these [2]catenanes revealed that a combination of [pi...pi] and [C-H...pi] interactions is responsible for the formation of supramolecular homodimers in the solid state. 1H NMR spectroscopic investigations of the four [2]catenanes demonstrated that supramolecular homodimers are also formed (Ka= 17-31M(-1), T= 185 K) in (CD3)2CO solutions. Dynamic 1H NMR spectroscopy revealed that the 1,5-dioxynaphtho[38]crown-10 and tetracationic cyclophane components in the four [2]catenanes and in the three [3]catenanes circumrotate (deltaGc(not equal to) = 9-14 kcal mol(-1)) through each other's cavity in (CD3)2CO. Similarly, the 1,5-dioxynaphthalene and the bipyridinium ring systems rotate (deltaGc(not equal to) =10-14 kcal mol(-1)) about their [O...O] and [N...N] axes, respectively, in solution.     

Assembly and autochirogenesis of a chiral inorganic polythioanion Möbius strip via symmetry breaking

Using [Mo(2)S(2)O(2)(H(2)O)(6)](2+) and squarate dianion, we synthesized the thiometalate ring compounds [(Mo(2)S(2)O(2))(x)(OH)(y)(C(4)O(4))(z)(Mo(2)O(8))(o)(H(2)O)(p)](n-), where [x,y,z,o,p,n] = [7,14,2,0,2,4] for 1, [6,8,2,2,4,8] for 2, and [4,6,1,1,0,4] for both 3a and 3b, which are chiral and nonchiral isomers, respectively. Not only do the four thiometalate clusters show decreasing symmetry at the molecular level across the series, but the incorporation of the "addendum" {Mo(2)O(8)}(o) unit also allows the thiometalate ring to twist. The reaction initially yields the chiral molecule 3a with a twisted ring, which undergoes spontaneous resolution upon crystallization; the reaction mixture later yields the intrinsically nonchiral isomer 3b with a nontwisted ring. In addition, the compounds are able to promote the electrocatalytic evolution of hydrogen.     

类钙钛矿结构新钽酸盐KSr2Ta3O10的合成、结构与层间特性

类钙钛矿结构氧化物是由钙钛矿结构基元与其它类型结构基元组合而成的一种超结构复合氧化物.     

Structural influences of organonitrogen ligands on vanadium oxide solids. Hydrothermal syntheses and structures of the terpyridine vanadates [V2O4(terpy)2]3[V10O28], [VO2(terpy)][V4O10], and [V9O22(terpy)3

Hydrothermal reactions of the V2O5/2,2':6':2"-terpyridine/ZnO/H2O system under a variety of conditions yielded the organic-inorganic hybrid materials [V2O4(terpy)2]3[V10O28].2H2O (VOXI-10), [VO2(terpy)][V4O10] (VOXI-11), and [V9O22(terpy)3] (VOXI-12). The structure of VOXI-10 consists of discrete binuclear cations [V2O4(terpy)2]2+ and one-dimensional chains [V10O28]6-, constructed of cyclic [V4O12]4- clusters linked through (VO4) tetrahedra. In contrast, the structure of VOXI-11 exhibits discrete mononuclear cations [VO2(terpy)]1+ and a two-dimensional vanadium oxide network, [V4O10]1-. The structure of the oxide layer is constructed from ribbons of edge-sharing square pyramids; adjacent ribbons are connected through corner-sharing interactions into the two-dimensional architecture. VOXI-12 is also a network structure; however, in this case the terpy ligand is incorporated into the two-dimensional oxide network whose unique structure is constructed from cyclic [V6O18]6- clusters and linear (V3O5(terpy)3) moieties of corner-sharing vanadium octahedra. The rings form chains through corner-sharing linkages; adjacent chains are connected through the trinuclear units. Crystal data: VOXI-10, C90H70N18O42V16, triclinic P1, a = 12.2071(7) A, b = 13.8855(8) A, 16.9832(10) A, alpha = 69.584(1) degrees, beta = 71.204(1) degrees, gamma = 84.640(1) degrees, Z = 1; VOXI-11, C15H11N3O12V5, monoclinic, P2(1)/n, a = 7.7771(1) A, b = 10.3595(2) A, c = 25.715(4) A, beta = 92.286(1) degrees, Z = 4; VOXI-12, C45H33N9O22V9, monoclinic C2/c, a = 23.774(2) A, b = 9.4309(6) A, c = 25.380(2) A, beta = 112.047(1) degrees, Z = 4.     

Preparation, characterization, and X-ray crystal structures of helical and syndiotactic zinc-based coordination polymers

The reactions of (facac)2Zn.2H2O (facac = 1,1,1,5,5,5-hexafluoroacetylacetonate) with 2,5-bis(4-ethynylpyridyl)furan (1) and 1,2-bis(4-ethynylpyridyl)benzene (2) yield, upon crystallization, coordination polymers. The former polymer, ((facac)2Zn.1)n, has an isotactic, helical structure in the solid state [monoclinic space group P2(1)/n; a = 11.0374(3) A, b = 24.2179(10) A, c = 14.3970(4) A, beta = 92.880(2) degrees; Z = 4]. The latter polymer, ((facac)2Zn.2)n, adopts a syndiotactic structure in the solid state [monoclinic space group P2(1)/n; a = 9.1344(1) A, b = 21.7985(5) A, c = 16.0322(4) A, beta = 99.6680(11) degrees; Z = 4]. The solution structures of the corresponding oligomers have been studied by low-temperature 1H and 19F NMR spectroscopy. Chiral polymers were prepared using the fragment [(+)-tfc]2Zn ((+)-tfc = 3-((trifluoromethyl)hydroxymethylene)-(+)-camphorate). A linear, zigzag structure was found for ([(+)-tfc]2Zn.1)n [triclinic space group P1; a = 7.4833(2) A, b = 14.1563(5) A, c = 21.21230(5) A, alpha = 78.4440(15) degrees, beta = 81.5644(15) degrees, gamma = 76.4976(13) degrees; Z = 1]. Reaction with tris(4-pyridyl)methanol (3) yielded a homochiral, helical polymer, ([(+)-tfc]2Zn.3)n [monoclinic space group C2; a = 25.0633(12) A, b = 11.8768(7) A, c = 17.1205(9) A, alpha = 90 degrees, beta = 117.954(3) degrees, gamma = 90 degrees; Z = 4].     

The preparation, structure and spectra properties of dual μ3-oxo bridged tetranuclear complexes containing the [CrnFe4-nO2]8+ core(n=0,2,4)

The preparation and characterization of [CrnFe4-nO2(O2CMe)7(bipy)2]Cl (1, n=0; 2, n=2; 3, n=4, bipy=2,2'-bipyridine) are described. The three complexes (1, 2 and 3) are obtained by tipyridine-mediated conversion of trinuclear [CrnFe3-nO(O2CMe)6(H2O)3]+(1, n=0; 2, n=1;3, n=3), and crystallized as three of approximate isomorphs. Crystal 2 is monoclinic with space group C2/c, a=27.454(5)A, b=11.789(1)A, c=16.570(3)A, B=118.78(1), V=4700.8A, z=4, u(MoKa)=11.64cm-1, F(000)=2056, final R=0.058 and Rw=0.066 for 3479 reflections with I > 3o(I). The Fe and Cr atoms in the cation are all +3 oxide state and disordered in the lattice, which is also supported by its Mossbauer studies. The [Cr2Fe2O2]8+ core can be thought of as being derived from two edge-sharing M3O units (M=Fe or Cr), and as a butterfly-like structure. The cations' structure of all three crystals are similar to each other and have C2 symmetry. The species are characterized by IR spectra and magnetic techniques, with particular emphasis on different