Two homochiral EuIII and SmIII enantiomeric pairs showing circularly polarized luminescence, photoluminescence and triboluminescence.

Two homochiral EuIII and SmIII tris(ß-diketonate) enantiomeric pairs, based on fluorinated ß-diketone (Hbtfa) and enantiopure asymmetric N,N'-donor ligands (LR and LS), Λ-Eu(btfa)3LR (R-1-Eu)/Δ-Eu(btfa)3LS (S-1-Eu) and Λ-Sm(btfa)3LR (R-2-Sm)/Δ-Sm(btfa)3LS (S-2-Sm) (btfa- = 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and LR/LS = (-)/(+)-4,5-pineno-2,2'-bipyridine) were synthesized. The electronic circular dichroism (ECD) spectra confirmed their enantiomeric nature. R-1-Eu/S-1-Eu and R-2-Sm/S-2-Sm exhibit intense characteristic emissions of EuIII (red) and SmIII (orange-red) ions both in the solid state and in DCM with long lifetimes and high luminescence quantum yields. For example, the overall quantum yields reach up to 61% and 53% along with very high sensitization efficiency values of 82 and 79 for R-1-Eu in the solid state and in DCM, respectively. Notably, the corresponding values are determined to be 6.5% (solid state) and 3.1% (DCM) for R-2-Sm, which are among the highest quantum yields for rare SmIII tris(ß-diketonate) luminescent complexes reported to date. Furthermore, R-1-Eu and R-2-Sm show a strong triboluminescence (TL) phenomenon visible with the naked eye in daylight. Moreover, R-1-Eu/S-1-Eu and R-2-Sm/S-2-Sm show circularly polarized luminescence (CPL) properties. Particularly, the luminescence dissymmetry factors (glum) for R-2-Sm/S-2-Sm are larger than those for R-1-Eu/S-1-Eu despite the fact that SmIII complexes usually show poorer emission than EuIII homologues, which is very rare in the reported EuIII and SmIII CPL-active complexes.

Double Negatively Curved C70 Growth through a Heptagon-Involving Pathway.

All previously reported C70 isomers have positive curvature and contain 12 pentagons in addition to hexagons. Herein, we report a new C70 species with two negatively curved heptagon moieties and 14 pentagons. This unconventional heptafullerene[70] containing two symmetric heptagons, referred to as dihept-C70 , grows in the carbon arc by a theoretically supported pathway in which the carbon cluster of a previously reported C66 species undergoes successive C2 insertion via a known heptafullerene[68] intermediate with low energy barriers. As identified by X-ray crystallography, the occurrence of heptagons facilitates a reduction in the angle of the π-orbital axis vector in the fused pentagons to stabilize dihept-C70 . Chlorination at the intersection of a heptagon and two adjacent pentagons can greatly enlarge the HOMO-LUMO gap, which makes dihept-C70 Cl6 isolable by chromatography. The synthesis of dihept-C70 Cl6 offers precious clues with respect to the fullerene formation mechanism in the carbon-clustering process.

Mononuclear Clusterfullerene Single-Molecule Magnet Containing Strained Fused-Pentagons Stabilized by a Nearly Linear Metal Cyanide Cluster.

Fused-pentagons results in an increase of local steric strain according to the isolated pentagon rule (IPR), and for all reported non-IPR clusterfullerenes multiple (two or three) metals are required to stabilize the strained fused-pentagons, making it difficult to access the single-atom properties. Herein, we report the syntheses and isolations of novel non-IPR mononuclear clusterfullerenes MNC@C76 (M=Tb, Y), in which one pair of strained fused-pentagon is stabilized by a mononuclear cluster. The molecular structures of MNC@C76 (M=Tb, Y) were determined unambiguously by single-crystal X-ray diffraction, featuring a non-IPR C2v (19138)-C76 cage entrapping a nearly linear MNC cluster, which is remarkably different from the triangular MNC cluster within the reported analogous clusterfullerenes based on IPR-obeying C82 cages. The TbNC@C76 molecule is found to be a field-induced single-molecule magnet (SMM).

Triangular Monometallic Cyanide Cluster Entrapped in Carbon Cage with Geometry-Dependent Molecular Magnetism.

Clusterfullerenes are capable of entrapping a variety of metal clusters within carbon cage, for which the entrapped metal cluster generally keeps its geometric structure (e.g., bond distance and angle) upon changing the isomeric structure of fullerene cage, and whether the properties of the entrapped metal cluster is geometry-dependent remains unclear. Herein we report an unusual triangular monometallic cluster entrapped in fullerene cage by isolating several novel terbium cyanide clusterfullerenes (TbNC@C82) with different cage isomeric structures. Upon varying the isomeric structure of C82 cage from C2(5) to Cs(6) and to C2v(9), the entrapped triangular TbNC cluster exhibits significant distortions as evidenced by the changes of Tb-C(N) and C-N bond distances and variation of the Tb-C(N)-N(C) angle by up to 20°, revealing that the geometric structure of the entrapped triangular TbNC cluster is variable. All three TbNC@C82 molecules are found to be single-ion magnets, and the change of the geometric structure of TbNC cluster directly leads to the alternation of the magnetic relaxation time of the corresponding TbNC@C82 clusterfullerene.

Formation of Curvature Subunit of Carbon in Combustion.

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.

Capturing the Fused-Pentagon C74 by Stepwise Chlorination.

As a bridge to connect medium-sized fullerenes, fused-pentagon C74 is still missing heretofore. Of 14 246 possible isomers, the first fused-pentagon C74 with the Fowler-Manolopoulos code of 14 049 was stabilized as C74Cl10 in the chlorine-involving carbon arc. The structure of C74Cl10 was identified by X-ray crystallography. The stabilization of pristine fused-pentagon C74 by stepwise chlorination was clarified in both theoretical simulation with density functional theory calculations and experimental fragmentation with multistage mass spectrometry.

Regioselective Oxidation of Fused-Pentagon Chlorofullerenes.

Two monoxides of typical smaller chlorofullerenes, (#271)C50Cl10O and (#913)C56Cl10O, featured with double-fused-pentagons, were synthesized to demonstrate further regioselective functionalization of non-IPR (IPR = isolated pentagon rule) chlorofullerenes. Both non-IPR chlorofullerene oxides exhibit an epoxy structure at the ortho-site of fused pentagons. In terms of the geometrical analysis and theoretical calculations, the principles for regioselective epoxy oxidation of non-IPR chlorofullerenes are revealed to follow both "fused-pentagon ortho-site" and "olefinic bond" rules, which are valuable for prediction of oxidation of non-IPR chlorofullerenes.

Synthesis of long-sought C66 with exohedral stabilization.

Previously reported fused-pentagon fullerenes stabilized by exohedral derivatization do not share the same cage with those stabilized by endohedral encapsulation. Herein we report the crystallographic identification of (#4348)C66Cl10, which has the same cage as that of previously reported Sc2@C66. According to the geometrical data of (#4348)C66Cl10, both strain relief (at the fused pentagons) and local aromaticity (on the remaining sp(2)-hybrided carbon framework) contribute to the exohedral stabilization of this long-sought 66 carbon atom cage.