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The combustion has long been applied for industrial synthesis of carbon materials such as fullerenes as well as carbon particles (known as carbon black), but the components and structures of the carbon soot are far from being clarified. Herein, we retrieve an unprecedented hydrofullerene C 66 H 4 from a soot of a low-pressure combustion of benzene-acetylene-oxygen. Unambiguously characterized by single-crystal X-ray diffraction, the C 66 H 4 renders a nonclassical geometry incorporating two heptagons and two pairs of fused pentagons in a C 2 v symmetry. The common vertexes of the fused pentagons are bonded with four hydrogen atoms to convert the hydrogen-linking carbon atoms from sp 2 to sp 3 hybridization, which together with the adjacent heptagons essentially releases the sp 2 -bond strains on the abutting-pentagon sites of the diheptagonal fused pentagon C 66 (dihept-C 66 ). DFT computations suggest the possibility for an in situ hydrogenation process leading to stabilization of the dihept-C 66 . In addition, the experiments have been carried out to study heptagon-dependent properties of dihept-C 66 H 4 , indicating the key responsibility of the heptagon for changing hydrocarbon activity and electronic properties. The present work with the unprecedented double-heptagon-containing hydrofullerene successfully isolated and identified as one of the low-pressure combustion products shows that the heptagon is a new building block for constructing fullerene products in addition to pentagons and hexagons in low-pressure combustion systems.

Curvature prevalently exists in the world of carbon materials (e.g., fullerenes, buckyl bowls, carbon nanotubes, and onions), but traditional C2-addition mechanisms fail to elucidate the mechanism responsible for the formation of carbon curvature starting from a pentagonal carbon ring in currently available chemical-physical processes such as combustion. Here, we show a complete series of nascent pentagon-incorporating C5-C18 that are online produced in the flame of acetylene-cyclopentadiene-oxygen and in situ captured by C60 or trapped as polycyclic aromatic hydrocarbons for clarifying the growth of the curved subunit of C20H10. A mechanism regarding C1-substitution and C2-addition has been proposed for understanding the formation of curvature in carbon materials, as exemplified by the typical curved molecule containing a single pentagon completely surrounded by five hexagons. The present mechanism, supported by the intermediates characterized by X-ray crystallography as well as NMR, has been experimentally validated for the rational synthesis of curved molecule in the commercially useful combustion process.

We carried out photopolymerization by [2 + 2] dimerization of a photoreactive guest molecule in the channels of a photoreactive porous coordination polymer. The photoreactions of the guest and two host ligands were monitored by single-crystal X-ray crystallography, providing snapshots of the interplay between the reactive centers. By correlating the structures of these three photocenters, a strong synergism was discovered among three reaction (quasi)equilibria and three types of photochemical reactions (isomerization, dimerization, and polymerization). This result indicates a strong coupling and feedback mechanism among the photocenters moderated by the coordination backbone.

Mass spectrometry with desorption electrospray ionization (DESI) is demonstrated to be useful for probing the strength of hydrogen bonding, exemplified by various complexes of benzothiazoles and carboxylic acids in the solid state. Efficiencies for fragmentation of the complexes, quantified by collision-induced dissociation (CID) technology, correspond well with energies of the hydrogen bonds of O-H···N and N-H···O bridging each pair of benzothiazole and carboxylic acid. Linear correlations (with correlation factors of 0.8953 and 0.9928) have been established for the calibration curves of normalized collision energy at 100% fragmentation rate vs the length between donor and acceptor (in the hydrogen bond of O-H···N) as well as the slope of the fragmentation efficiency curve vs the average length difference between O-H···N and N-H···O in the complex. The mechanism responsible for determination of the hydrogen bonds is proposed on the basis of the experiments starting from the mixtures of the complexes as well as labeling with deuterium. As a complement of previously available methods (e.g., X-ray diffraction analysis), expectably, the proposed mass spectrometric method seems to be versatile for probing hydrogen bond energies.

Four 52-metal-ion 3d-4f cluster complexes featuring a common core of Ln(42)M(10) (Ln = Gd(3+), Dy(3+); M = Co(2+/3+), Ni(2+)) were obtained through self-assembly of the metal ions templated by mixed anions (ClO(4)(-) and CO(3)(2-)). Magnetic studies revealed that the Gd(42)Co(10) and Gd(42)Ni(10) clusters exhibit the largest magnetocaloric effect (MCE) among any known 3d-4f complexes. Replacement of Gd(3+) ions with anisotropic Dy(3+) ions caused significant changes in the magnetic behavior of the clusters; both Dy(42)Co(10) and Dy(42)Ni(10) displayed slow relaxation of the magnetization.

A long-sought empty non-IPR fullerene, (#11188)C72, which is more stable than the sole IPR isomer in the fullerene[72] family, has been retrieved and crystallographically characterized as (#11188)C72Cl4. Mass spectrometric data support the facile dechlorination of (#11188)C72Cl4 and, in turn, the possible stability of pristine (#11188)C72.

For the first time an easier, operable combustion method is employed for the synthesis of non-IPR fullerene, and an octahydro[60]fullerene with a non-IPR C(60) cage (C(60) isomer (#1809)C(60)) produced by combustion is isolated and characterized by MS, UV-vis, IR, and NMR spectroscopies in combination with DFT calculations. This finding shows that, in addition to chlorine, hydrogen can be an ample cataloreactant for the production of non-IPR fullerene derivatives under such conditions as arc-burning and diffusion combustion.

C(78) is one of the most widely investigated higher fullerenes. Among its huge isomer family, only one non-IPR (IPR = isolated pentagon ring) cage, the C(2)-symmetric (#22010)C(78), was previously stabilized by endohedral derivatization. Here we report a new C(1)-symmetric non-IPR hollow isomer, (#23863)C(78), which was captured as (#23863)C(78)Cl(8) and then subjected to a regioselective substitution reaction with benzyl hydroperoxide to form (#23863)C(78)(OOCH(2)C(6)H(5))Cl(7). The structural connectivity of (#23863)C(78), which contains a pair of fused pentagons, was confirmed by single-crystal X-ray diffraction analysis of the (#23863)C(78)(OOCH(2)C(6)H(5))Cl(7) molecule, which shares the same fullerene core with (#23863)C(78)Cl(8); support for the structure is provided by comparable IR measurements and computation. Theoretical studies suggest that the differences in C-Cl bond length, intermediate stability, and steric effects of the involved molecules account for the chemical regioselectivity of the substitution reaction.

The long-sought-after crystal structure of Fe(tpa)(NCS)(2) (1, tpa = tris(2-pyridylmethyl)amine), an otherwise well-studied spin-crossover (SCO) complex, has been obtained, and its one-step, incomplete spin transition was correlated to its solid-state structures at different temperatures. Upon exposure to methanol vapor, single-crystal-to-single-crystal transformation of 1 to a new SCO compound, 2, formulated as {[Fe(tpa)(NCS)(2)] x [Fe(tpa)(NCS)(2) x CH(3)OH]}, occurs with a dramatic color change from yellow to red. Crystallographic studies revealed that the asymmetric unit of the structure of 2 contains two independent Fe(II) centers. Studies by magnetic measurements and Mossbauer spectroscopy revealed a two-step complete spin transition for compound 2, between LS-LS and HS-HS, via an unambiguous intermediate LS-HS phase; the two SCO centers of disparate spin states were resolved crystallographically. That a significant portion of the original crystal structure is maintained indicates that the present approach is a more subtle means of altering the properties associated with SCO phenomenon than by changing counteranions or crystallization using different solvents. Furthermore, the dramatic changes in crystal structure and SCO behaviors triggered by mere solvent sorption suggest that this approach is rather efficient in modifying and hopefully fine-tuning and optimizing properties of SCO compounds. Coupled with the aforementioned gentleness and subtlety, the present approach of heterogeneously introducing perturbations to pre-existing supramolecular arrays of SCO units is more conducive to systematic studies aiming at the discovery of new SCO systems and phenomenon toward their ultimate materials applications.

A smaller fullerene C56 (#913) is stabilized, isolated, and crystallographically characterized as C56Cl10. The geometric parameters of C56Cl10 imply the otherwise unstable cage of C56 can be stabilized by chlorination through releasing its surface strains and maintaining fragmental aromaticity. An unexpected C Cl...ClC short contact, as well as the linear alignment with pearl-necklace-shaped, is revealed in C56Cl10 crystal.

A novel single-chain magnet, [MnIII3O(Meppz)3(EtOH)4(OAc)] (1), has been successfully synthesized from a secondary building block [MnIII3O(Meppz)3(EtOH)5Cl] (2) with an S = 1 ground state. SCM 1 exhibits both magnetization relaxation and dielectric relaxation properties.

Epitaxial growth, as a best strategy to attain a heterostructure with a well-defined and clean interface, usually takes place on a planar substrate. In this paper, using a ZnO/SnO2 core-shell heterostructure as an example, we demonstrate the possibility of establishing a three-dimensional epitaxial interface between two materials with different crystal systems for the first time and show possible tailoring optical properties by building the heteroepitaxial crystal interface. The characterization results of element mapping, high-resolution transmission electron microscopy, and selected area electric diffraction reveal that the as-prepared ZnO/SnO2 heterostructure has a tetrapod-like ZnO core and a SnO2 shell with 15-30 nm, and their special epitaxial relation is (010)SnO2//(010)ZnO and [100]SnO2//[0001]ZnO. Such three-dimensional epitaxy between the ZnO core and SnO2 shell is quite different from the usual planar epitaxy or three-dimensional epitaxy between materials having the same crystal structure. A rational model of such complicated epitaxy has been proposed through investigating the certain structural comparability between the wurtzite ZnO and rutile SnO2 crystals. The as-prepared T-ZnO/SnO2 epitaxial heterostructure exhibits unique luminescence properties in contrast with individual tetrapod ZnO and SnO2 nanostructures, in which the epitaxial interface induces new luminescence properties. This result may inspire great interest in exploring other complicated epitaxy systems and their potential applications in laser, gas sensor, solar energy conversion, photo catalysis, and nanodevices in the future.