Molecular complex of C60 fullerene with an organic π-donor,bis(methylenedithiotetrathiafulvalene): synthesis,crystal structures,and properties

A new molecular complex based on [60]fullerene, namely, (BMDT-TTF)·C₆₀·2CS₂ (1) (where BMDT-TTF is bis(methylenedithiotetrathiafulvalene)) was synthesized. The molecular and crystal structures of 1 were established by X-ray diffraction analysis. Complex 1 has a layered structure, layers of C₆₀ molecules alternating with those formed by BMDT-TTF molecules and CS₂ molecules located between them. In complex 1, there are short contacts between C₆₀ and the donor molecules, which results in a changed BMDT-TTF geometry. The donor molecules in 1 form in addition short S...S contacts. The data of IR spectroscopy indicate that the charge transfer to the fullerene molecule is insignificant if at all present. The conductivity of a single crystal of 1 measured at 20 °C using a four-contact method is 2·10^–5 ( cm)^–1.     

Crystal and molecular structures of fluorinated derivatives of C60 fullerene

Two solvates of fluorinated derivatives of C₆₀ fullerene were studied by single-crystal X-ray diffraction analysis. The crystals of fluorinated fullerene solvate C₆₀F₁₈·C₆H₅Me belong to the monoclinic system with the unit cell parameters a = 11.532(2) , b = 21.501(3) , c = 16.261(2) , = 101.798(5)°. The fluorinated fullerene molecule with the approximate symmetry C _3v occupies a general position. The crystals of fluorinated fullerene solvate C₆₀F₄₈·2C₆H₃Me₃ belong to the cubic system (a = 23.138(2) ). The C₆₀F₄₈ molecule occupies the special position with the S ₆ symmetry. The experimental molecular geometry agrees with the results of quantum-chemical calculations.     

Classical Valence Similarity in Fullerene Derivatives

Summary.  The generalized Pauling bond order was enumerated in the C₆₀ fullerene cage molecule (truncated icosahedral symmetry). This index measures chemical similarity in fullerene derivatives such as dihydrofullerene (C₆₀H₂), anionized monohydrofullerene (C₆₀H⁻), N-substituted monohydrofullerene (C₅₉NH), the fullerene dimer ((C₆₀)₂), and the dianionic fullerene dimer ((C₆₀)₂ ²⁻). It is also useful in judging the chemical stability of isomers. Received October 9, 2001. Accepted November 9, 2001     

Influence of intermolecular hydrogen bonding on magnetic properties of mononuclear cobalt and nickel pivalates with amidine ligands

The magnetic properties of the mononuclear cobalt(ii) amidine complex Co(Me₃CCOO)₂{H₂N(C₅H₃N)NH(MeC=NH} (1) having a tetrahedral structure and its solvate 1·HOOCCMe₃·0.5C₆H₆ (1a) are substantially different. Complex 1 possesses ferromagnetic properties and exhibits residual magnetization at liquid-helium temperatures, whereas solvate 1a and the octahedral amidine complex Ni(Me₃CCOO)₂{H₂N(C₅H₃N)NH(MeC=NH}·MeCN (3·MeCN) show antiferromagnetic properties. Apparently, this is associated with the difference in the type of intermolecular nonbonded interactions in the crystals of 1, 1a, and 3·MeCN, which form channels for spin-spin exchange. The tetrahedral isostructural mononuclear complexes ML₂ (M = Co (5), Ni (6), L is N-tosyl-2,5-dimethyl-8-aminoquinoline) were synthesized. These complexes exhibit antiferromagnetic properties.     

Quantum chemical studies of non-covalent interactions between the ethyl cation and rare gases

By taking into consideration the facts that rare gases (Ar, He, Kr, and Ne) are practically inert and that the structure of the ethyl cation (C₂H₅⁺) is stabilized through the hyperconjugation effect, a theoretical study at the B3LYP/6-311 + +G(d,p) level of calculation was carried out here in order to investigate the formation of the C₂H₅⁺···Ar, C₂H₅⁺···He, C₂H₅⁺···Kr, and C₂H₅⁺···Ne complexes. The charge transfers among H and Ar, He, Kr or Ne prove that the loss of electronic density on the rare gases are clearly noticeable. Additionally, the synergism between the structural changes and the vibration shifts have been demonstrated and justified on the basis of the Bent rule and QTAIM calculations. In complement, the interaction strength in H⁺···Ar, H⁺···He, H⁺···Kr, and H⁺···Ne was examined, although the covalent character is completely null because these contacts are very weak.     

Cycloaddition of C60 fullerene to stable 2-RSO2-benzonitrile oxides

The interaction of stable 2-RSO₂-benzonitrile oxides1a−c (R=Ph, Bu^t, or PhMeN) with C₆₀ fullerene proceeds at the double (6,6)-bond of fullerene as the [3+2] cycloaddition to form the corresponding isoxazolines2a−c. The molecular structure of compound2b was established by X-ray structural analysis. The interaction of C₆₀ fullerene with 2-(5-methyl-4-nitrothiophene)carbonitrile sulfide, which was obtained by thermolysis of 5-(5′-methyl-4′-nitro-2′-thienyl)1,3,4-oxathiazol-2-one, affords only unstable products. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 118–126, January, 1997.     

Chemiluminescence produced by oxidation of fullerene hydride C60H36 with oxygen in solution

It was found that the oxidation of fullerene hydride C₆₀H₃₆ with oxygen in solution is accompanied by chemiluminescence (CL). The CL spectrum maxima are assigned to the emission by the oxidation products of C₆₀H₃₆, namely, the excited hydride C₆₀H₁₈* (495, 535 nm) and singlet-excited fullerene ¹C₆₀* (720—750 nm).     

Heterometallic zirconocene(iii) aluminum hydride complex (Cp2ZrH)2HAlCl2·C4H8O2·C6H6

The heterometallic zirconocene(iii) aluminum hydride complex (Cp₂ZrH)₂HAlCl₂·C₄H₈O₂·C₆H₆ was synthesized by reduction of Cp₂ZrCl₂ with lithium aluminum hydride in the presence of Cp₂TiBH₄ and 1,4-dioxane, and its structure was established by X-ray diffraction analysis.     

Structural Diversity of Silver Clusters in Double and Triple Salts of Silver Acetylide with Silver Perfluoro-Dicarboxylates

The reactions of Ag₂C₂ and the corresponding silver perfluoro-dicarboxylates result in the formation of three new double and triple salts, Ag₂C₂·3AgO₂CCF₂CF₂CO₂Ag·7H₂O (1), 2Ag₂C₂·6AgO₂CCF₂CF₂CO₂Ag·AgNO₃·12H₂O (2) and Ag₂C₂·4AgO₂CCF₂CF₂CF₂CO₂Ag·17.5H₂O (3), which have been structurally characterized by single crystal X-ray analysis. Their structures contain silver cages of various shapes: crown in 1, pentagonal bipyramid together with monocapped pentagonal bipyramid in 2, and square antiprism in 3, each containing an encapsulated acetylide dianion. Except for the pentagonal bipyramid, the other three silver cages are unprecedented. Compound 2 provides a unique example in which two kinds of silver polyhedra with different numbers of vertices (C₂@Ag₇ and C₂@Ag₈) co-exist in the crystal structure.     

Preparation and study of hydrides of fullerenes C60 and C70

Fullerene hydrides were prepared by hydrogenation of fullerences C₆₀ and C₇₀ using proton transfer from 9,10-dihydroanthracene to fullerene and were studied by mass spectrometry (electron impact, field desorption), IR, UV, and¹H and¹³C NMR spectroscopy. The main product of the hydrogenation of C₆₀ is C₆₀H₃₆, which is sufficiently stable. Hydrogenation of fullerene C₇₀ gives a series of polyhydrides C₇₀H _n (n=36–46), and the main product is C₇₀H₃₆. The dehydrogenation of C₆₀H₃₆ by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is not quantitative and results in the formation of fullerene derivatives along with C₆₀. The comparison of the IR and¹H and¹³C NMR spectral data for solid C₆₀H₃₆ with the theoretical calculations suggests that the fullerene hydride has aT-symmetric structure and contains four isolated benzenoid rings located at tetrahedral positions on the surface of the closed skeleton of the molecule. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 4, pp. 671–678, April, 1997.     

Addition of Me2·CCN,Me2·CPh,and CCl3CH2·CHPh radicals to fullerene C60

The rate constants for addition of the Me₂ ^·CCN, Me₂ ^·CPh, and CCl₃CH₂ ^·CHPh radicals to fullerene C₆₀ at 22 °C were determined by ESR spectroscopy using spin trapping technique.     

Crystal Structures of 1,5,9,18,22,26-Hexaaza[11.11]-p-cyclophane Adducts; Two-dimensional Supramolecular Networks

Two newly identified supramolecular structures arise from self-assembly of the macrocyclic 1,5,9,18,22,26- hexaaza[11.11]-p-cyclophane salts with o-nitrophenol (C₂₈H₅₀N₆)⁴⁺·4(C₆H₄NO₂O)⁻ (1) and with HCl (C₂₈H₅₂N₆)⁶⁺·6Cl^-·4H₂O (2). In both cases two-dimensional supramolecular sheets are formed.     

单加成环丙烷富勒烯膦酸酯衍生物的合成与电化学性能

在Mn(OAc)₃•2H₂O催化下, C₆₀分别和亚甲基二膦酸四乙酯、氰基亚甲基膦酸二乙酯或乙氧羰基亚甲基膦酸二乙酯在氯苯中回流, 生成3个单加成环丙烷富勒烯膦酸衍生物C₆₀C(R)PO(OEt)₂ [1, R＝PO(OEt)₂; 2, R＝COOEt; 3, R＝CN]. 与以前报道的Bingel反应法相比, 该方法副产物少并且缩短了反应时间. 采用循环伏安法发现1, 2的还原电位相对于C₆₀发生负移, 而3的还原电位相对于C₆₀却正移40 mV, 表明引入象氰基一样具有很强吸电子能力的取代基团, 可以改善富勒烯球的电化学性能, 合成电子接受能力较强的富勒烯衍生物.     

Entwässerung von ZnSO4·7H2O durch organische Lösungsmittel und unter Hochvakuum

Zusammenfassung In der vorliegenden Arbeit wurde der Entwässerungsprozeß von ZnSO₄·7 H₂O mit organischen Lösungsmitteln bei Raum-temperatur sowie unter Hochvakuum bei 20, 60, 100 und 140°C untersucht und die Strukturveränderungen mit Hilfe von IR-Spektren und Röntgenpulverdiagrammen diskutiert. Mit C₂H₅OH (99,2%) oder Aceton führt die Entwässerung in 30 Minuten zu ZnSO₄·6 H₂O und nach mehreren Stunden zu einer Mischung von ZnSO₄·6 H₂O und ZnSO₄·H₂O. Mit Xylol beobachtet man diesen Prozeß nicht. Unter Hochvakuum gelangt man bei 20°C in 46 Stdn. und bei 60°C in 16 Stdn. zu ZnSO₄·H₂O, bei 140°C im Verlaufe von 24 Stdn. bis zu wasserfreiem ZnSO₄.

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Desiccation of ZnSO₄·7 H₂Owith organic solvents and under high vacuum

In this paper the desiccation process of ZnSO₄·7 H₂O with organic solvents at room temperature and under high vacuum at 20, 60, 100, and 140°C was investigated. The structural changes were discussed by means of IR-spectra and X-ray powder diagrams. With C₂H₅OH (99.2%) or acetone the desiccation leads within 30 minutes to ZnSO₄·6 H₂O and after several hours to a mixture of ZnSO₄·6 H₂O and ZnSO₄·H₂O. With xylene this process in praxi does not exist. Under high vacuum one reaches ZnSO₄·H₂O at 20°C within 46 hours and at 60°C within 16 hours. ZnSO₄ is free of water at 140°C within 24 hours.

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Mit 4 Abbildungen     

Spin-adducts of radicals ·P(O)(OPri)2 and ·CMe3 with pyrrolidino[60]fullerenes studied by ESR spectroscopy

The addition of the ^·Bu^t (R¹) and ^·P(O)(OPrⁱ)₂ (R²) radicals to pyrrolidino[60]fullerenes C₆₀CH₂NMeCHX (X = C₆H₄N(CH₂CH₂Cl)₂, 2,6-(Bu^t)₂C₆H₂OH, PhC₆H₄, and indol-3-yl) was studied by ESR spectroscopy. The rate constants of R¹ radical addition to these compounds and dimerization of spin-adducts of the R¹ radicals with pyrrolidino[60]fullerenes were determined. Pyrrolidino[60]fullerenes manifest considerably higher reactivity toward the R¹ radicals than fullerene C₆₀ and methanofullerenes C₆₀CX¹X² (X¹ = X² = CO₂Et; X¹ = CO₂Me, X² = OP(OMe)₂, X¹ = X² = OP(OEt)₂).     

Thermodynamic properties of fullerene C60 solutions in a mixture of tetrachloromethane and toluene

The solubility of fullerene C₆₀ in the tetrachloromethane-toluene system is measured over the entire range of compositions of the mixed solvent in the temperature range 298.15–338.15 K. An equation is proposed for describing the solubility of C₆₀ as a function of the temperature and the composition of the mixed solvent. The equation is used for calculating the thermodynamic characteristics of solution of the fullerene. It is found that, in the investigated C₆₀-CCl₄/C₆H₅CH₃ system, two types of solid solvates of the fullerene with the solvent are formed. The enthalpies and temperatures of incongruent melting of the crystalline solvates are determined by differential scanning calorimetry. The thermodynamic characteristics of solution and solvation of C₆₀ in CCl₄ and C₆H₅CH₃ are obtained. It is shown that the entropy factor plays a decisive role in the temperature dependence of the Gibbs energy of solvation of the fullerene.     

Kinetic regularities of conversion of ozone complexes with arenes

The kinetic regularities of conversion of ozone complexes with several substituted benzenes (ArX = C₆H₅Me, C₆H₅Et, C₆H₅CHMe₂, C₆H₅CMe₃, C₆H₅F, C₆H₅Cl,m-BrC ₆ H ₅ Me, and C₆H₅CH₂Cl) were studied by spectrophotometry. The rate of consumption of [ArX · O₃ in a CH₂Cl₂-ArX solution obeys the kinetic equationW =k ₀[ArX · O₃]+k ₁ [ArX · O3][ArX]. The values of the rate constants ko andk ₁for the complexes studied were determined at -60+0 °C.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 371–374, 'February, 1996.     

Verbindungen der Seltenerdelemente mit α-4-Dimethylaminobenzoinoxim

Zusammenfassung Es wurden VerbindungenLnCl₃·H₂ DBox ^* (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb) und La₂(DBox)₃·6 CH₃OH, Pr₂(DBox)₃·6 CH₃OH, Nd₂(DBox)₃·3 C₂H₅OH, Sm₂(DBox)₃· ·3 C₂H₅OH, Gd₂(DBox)₃·3 C₂H₅OH, Tb₂(DBox)₃·2 C₂H₅OH, DyH(DBox)₂·2 C₂H₅OH, HoH(DBox)₂·2 C₂H₅OH, ErH(DBox)₂, YH(DBox)₂·H₂O isoliert. Diese wurden mittels Thermoanalyse und Röntgenstreuung untersucht sowie ihre IR-Absorptionspektren gemessen und diskutiert.

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Compounds of rare earth elements with -4-dimethylaminobenzoinoxime

The compoundsLnCl₃·H₂ DBox ^* (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb) and La₂(DBox)₃·6 CH₃OH, Pr₂(DBox)₃·6 CH₃OH, Nd₂(DBox)₃·3 C₂H₅OH, Sm₂(DBox)₃·3 C₂H₅OH, Gd₂(DBox)₃· ·3 C₂H₅OH, Tb₂(DBox)₃·2 C₂H₅OH, DyH(DBox)₂·2 C₂H₅OH, HoH(DBox)₂·2 C₂H₅OH, ErH(DBox)₂ and YH(DBox)₂·H₂O were isolated, and studied by thermoanalysis and X-ray diffraction. Their IR absorption spectra were recorded and are discussed.

     

Quenching excited triplet C60 fullerene by tetracyanoethylene in benzonitrile

Quenching excited triplet³C₆₀ fullerene by tetracyanoethylene (TCNE) in a benzonitrile solution proceeds with a rate constant equal to (4.2±0.3) · 10¹⁸ (M · s)^–1. The formation of a radical ion pair [C₆₀ ⁺ · · · TCNE^–] was observed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1228–1230, July, 1993.