Negative Volume Compressibility in Sc3N@C80-Cubane Cocrystal with Charge Transfer.

According to the laws of thermodynamics, materials normally exhibit contraction or expansion along the directions of the applied pressure or tension. Here, we show that a man-made cocrystal of a metallofullerene and highly energetic cubane, with strained sp3 bonding, may exhibit an anomalous negative volume compressibility. In this cocrystal, the freely rotating fullerene Sc3N@C80 acts as a structural building block while static cubane molecules fill the lattice interstitial sites. Under high pressure, Sc3N@C80 keeps stable and preserves the crystalline framework of the materials, while the cubane undergoes a progressive configurational transformation above 6.5 GPa, probably promoted by charge transfer from fullerene to cubane. A further configurational change of the cubane into a low-density configuration at higher pressure results in an anomalous pressure-driven lattice expansion of the cocrystal (∼1.8% volume expansion). Such unusual negative compressibility has previously only been predicted by theory and suggested to appear in mechanical metamaterials.

From Methyl Radical to Polyacetylene: Size-Dependent Structural Properties of Linear Polyenes.

Hydrocarbons and nanostructures, consisting of trigonally coordinated C-atoms, represent a huge family of functional materials. Depending on the configuration and the size, they may be highreactivity intermediates, raw materials or catalyzers of organic reactions, or semiconducting polymers with variable bandgap. Small molecules have been intensively studied by chemists, and crystalline polymers by physicist, but the knowledge on the medium-size oligomers is rather incomplete. For a better understanding of such materials, the size-dependence of several structural properties of linear polyenes and infinite polymers were calculated at the same level of density functional theory. Linear polyenes are the simplest derivatives of trigonal carbon and their study is instructive for the understanding of more complicated series. The analysis of heats of formation and bondlength distributions reveals a singlet-triplet transition in the trans-cisoid polyenes at the carbon number of n = 28. An efficient method is suggested for the common treatment of the molecular orbitals of polyenes and the energy bands of polyacetylene: the mapping of the energy levels of polyenes to the bands of polyacetylene. The excellent agreement of the levels of molecular orbitals and the polymer bands makes possible the reconstruction of the bands in the knowledge of molecular orbitals and vice versa. A future extension of the suggested mapping to 2 dimensions may be suitable for a uniform treatment of trigonal carbon systems from methyl radical through polycyclic aromatic hydrocarbons to graphene.

Crystal structure of the 4 + 2 cyclo-adduct of photooxidized anthracene and C60 fullerene.

The structure of the title compound, 5,6-[(1R,10S)-2,9-dioxatri-cyclo-[8.6.0(3,8).0(11,16)]hexa-decane-1,10-di-yl]-(C60-Ih)[5,6]fullerene methane-dithione 0.1-solvate, C74H10O2·0.1CS2, has tetra-gonal (P42/n) symmetry at 100 K. It has a unique eight-membered ring, with two incorporated O atoms in place of the original central ring of the anthracene. The distortion of the mol-ecular geometry around the cyclo-adduct bonds corresponds to that seen in related fullerene derivatives. Close packing of the adduct forms cavities partially filled with disordered carbon di-sulfide solvent mol-ecule. The 41% occupancy of the cavities yields an overall 1:0.103 adduct-solvent ratio. Reaction steps are described as light-assisted singlet-oxygen generation, peroxide, epoxide and dioxocin derivative formation and the final step of thermally activated cyclo-addition.

Orientational ordering and low-temperature libration in the rotor-stator cocrystals of fullerenes and cubane.

Cocrystals of cubane and fullerenes, C60-cubane and C70-cubane, show distinct rotational ordering transitions. We studied the corresponding structural changes with temperature-dependent X-ray diffraction and the thermodynamics of the phase transitions with adiabatic microcalorimetry and differential scanning calorimetry. C60-cubane has one phase transition around 130 K from a high-temperature fcc phase with freely rotating C60 to a low-temperature orthorombic phase in which the fullerene rotation is frozen. The corresponding enthalpy change is approximately 1170 J/mol, and the entropy change is 9.6 J/(mol K). C70-cubane has two phase transitions. Around 380 K, the high-temperature fcc phase with freely rotating C70 transforms into a bct phase in which the C70 rotates uniaxially around an axis that precesses around the c direction with a full opening angle of 40 degree. Around 170 K, the uniaxial rotation also freezes out, with an accompanying structural transition to monoclinic and enthalpy and entropy changes of 620 J/mol and 8.7 J/(mol K), respectively. The low-temperature specific heat was analyzed in terms of the Debye-Einstein model to estimate the librational energies of the fullerenes and Debye temperatures. We found very similar values for the two cocrystals, approximately Elib = 2.2 meV and TDebye = 23 K. For reference, we also measured the specific heats of pure C60 and C70 and found Elib = 2.96 meV and TDebye = 32 K for C60 and Elib = 1.9 meV and TDebye = 20 K for C70.

New Ordered Structure of Amorphous Carbon Clusters Induced by Fullerene-Cubane Reactions.

As a new category of solids, crystalline materials constructed with amorphous building blocks expand the structure categorization of solids, for which designing such new structures and understanding the corresponding formation mechanisms are fundamentally important. Unlike previous reports, new amorphous carbon clusters constructed ordered carbon phases are found here by compressing C8 H8 /C60 cocrystals, in which the highly energetic cubane (C8 H8 ) exhibits unusual roles as to the structure formation and transformations under pressure. The significant role of C8 H8 is to stabilize the boundary interactions of the highly compressed or collapsed C60 clusters which preserves their long-range ordered arrangement up to 45 GPa. With increasing time at high pressure, the gradual random bonding between C8 H8 and carbon clusters, due to "energy release" of highly compressed cubane, leads to the loss of the ability of C8 H8 to stabilize the carbon cluster arrangement. Thus a transition from short-range disorder to long-range disorder (amorphization) occurs in the formed material. The spontaneous bonding reconstruction most likely results in a 3D network in the material, which can create ring cracks on diamond anvils.

Structure of the crystalline C60 photopolymer and the isolation of its cycloadduct components.

We produced C60 photopolymer in gram quantity by a new monomer recycling method and extracted its soluble components. The most abundant components, the (2 + 2) cycloadduct dimer, C120, and several oligomers were isolated by high-performance liquid chromatography (HPLC). Three different C180 isomers were identified on the basis of their formation and decomposition reactions. The crystal structure of the insoluble photopolymer is face-centered cubic (fcc) with a contracted lattice parameter relative to the pristine C60. The lattice parameter and the amounts of soluble oligomers depend on the preparation temperature. We explain this variation with a topochemical model of photopolymerization: The geometrical conditions allow the formation of only linear or planar oligomers in the triangular or square sublattices. Competing reactions in the intersecting planes prevent the formation of large oligomers. The lattice contraction is proportional to the number of cycloadduct bonds.

Rotor-stator molecular crystals of fullerenes with cubane.

Cubane (C8H8) and fullerene (C60) are famous cage molecules with shapes of platonic or archimedean solids. Their remarkable chemical and solid-state properties have induced great scientific interest. Both materials form polymorphic crystals of molecules with variable orientational ordering. The idea of intercalating fullerene with cubane was raised several years ago but no attempts at preparation have been reported. Here we show that C60 and similarly C70 form high-symmetry molecular crystals with cubane owing to topological molecular recognition between the convex surface of fullerenes and the concave cubane. Static cubane occupies the octahedral voids of the face-centred-cubic structures and acts as a bearing between the rotating fullerene molecules. The smooth contact of the rotor and stator molecules decreases significantly the temperature of orientational ordering. These materials have great topochemical importance: at elevated temperatures they transform to high-stability covalent derivatives although preserving their crystalline appearance. The size-dependent molecular recognition promises selective formation of related structures with higher fullerenes and/or substituted cubanes.