For the first time, actinide endohedral metallofullerenes (EMFs) with non-isolated-pentagon-rule (non-IPR) carbon cages, U@C80, Th@C80, and U@C76, have been successfully synthesized and fully characterized by mass spectrometry, single crystal X-ray diffractometry, UV–vis–NIR and Raman spectroscopy, and cyclic voltammetry. Crystallographic analysis revealed that the U@C80 and Th@C80 share the same non-IPR cage of C 1(28324)-C80, and U@C76 was assigned to non-IPR U@C 1(17418)-C76. All of these cages are chiral and have never been reported before. Further structural analyses show that enantiomers of C 1(17418)-C76 and C 1(28324)-C80 share a significant continuous portion of the cage and are topologically connected by only two C2 insertions. DFT calculations show that the stabilization of these unique non-IPR fullerenes originates from a four-electron transfer, a significant degree of covalency, and the resulting strong host–guest interactions between the actinide ions and the fullerene cages. Moreover, because the actinide ion displays high mobility within the fullerene, both the symmetry of the carbon cage and the possibility of forming chiral fullerenes play important roles to determine the isomer abundances at temperatures of fullerene formation. This study provides what is probably one of the most complete examples in which carbon cage selection occurs through thermodynamic control at high temperatures, so the selected cages do not necessarily coincide with the most stable ones at room temperature. This work also demonstrated that the metal–cage interactions in actinide EMFs show remarkable differences from those previously known for lanthanide EMFs. These unique interactions not only could stabilize new carbon cage structures, but more importantly, they lead to a new family of metallofullerenes for which the cage selection pattern is different to that observed so far for nonactinide EMFs. For this new family, the simple ionic A q+@C2n q– model makes predictions less reliable, and in general, unambiguously discerning the isolated structures requires the combination of accurate computational and experimental data.

First X-ray structures and metal oxidation state dependence on cage isomerism for U-EMFs.

The dual-emissive N, S co-doped carbon dots (N, S-CDs) with a long emission wavelength were synthesized via solvothermal method. The N, S-CDs possess relatively high photoluminescence (PL) quantum yield (QY) (35.7%) towards near-infrared fluorescent peak up to 648 nm. With the advanced characterization techniques including X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), etc. It is found that the doped N, S elements play an important role in the formation of high QY CDs. The N, S-CDs exist distinct pH-sensitive feature with reversible fluorescence in a good linear relationship with pH values in the range of 1.0-13.0. What is more, N, S-CDs can be used as an ultrasensitive Ag + probe sensor with the resolution up to 0.4 μM. This finding will expand the application of as prepared N, S-CDs in sensing and environmental fields.

Tubular higher fullerenes are prototypes of finite-length end-capped carbon nanotubes (CNTs) whose structures can be accurately characterized by single-crystal X-ray diffraction crystallography. We present here the isolation and crystallographic characterization of two unprecedented higher fullerenes stabilized by the encapsulation of a La2C2 cluster, namely, La2C2@Cs(574)-C102, which has a perfect tubular cage corresponding to a short (10, 0) zigzag carbon nanotube, and La2C2@C2(816)-C104 which has a defective cage with a pyracylene motif inserting into the cage waist. Both cages provide sufficient spaces for the large La2C2 cluster to adopt a stretched and nearly planar configuration, departing from the common butterfly-like configuration which has been frequently observed in midsized carbide metallofullerenes (e.g., Sc2C2@C80-84), to achieve strong metal-cage interactions. More meaningfully, our crystallographic results demonstrate that the defective cage of C2(816)-C104 is a starting point to form the other three tubular cages known so far, i.e., D5(450)-C100, Cs(574)-C102, and D3d(822)-C104, presenting evidence for the top-down formation mechanism of fullerenes. The fact that only the large La2C2 cluster has been found in giant fullerene cages (C>100) and the small clusters M2C2 (M = Sc, Y, Er, etc.) are present in midsized fullerenes (C80-C86) indicates that geometrical matching between the cluster and the cage, which ensures strong metal-cage interactions, is an important factor controlling the stability of the resultant metallofullerenes, in addition to charge transfer.

We demonstrate that a finite-length (10,0) carbon nanotube (CNT) with two fullerene caps, namely D5(450)-C100, is an ideal prototype to study the mechanical responses of small CNTs upon endohedral metal doping. Encapsulation of a large La2C2 cluster inside D5(450)-C100 induces a 5% axial compression of the cage, as compared with the structure of La2@D5(450)-C100. Detailed crystallographic analyses reveal quantitively the flexibility of the [10]cyclacene-sidewall segment and the rigidity of the pentagon-dominating caps for the first time. The internal C2-unit acts as a molecular spring that attracts the surrounding cage carbon atoms through strong interactions with the two moving lanthanum ions. This is the first crystallographic observation of the axial compression of CNTs caused by the internal stress, which enhances our knowledge about the structural deformation of novel carbon allotropes at the atomic level.

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Conspectus Fullerene carbon cages can encapsulate a wide variety of atoms, ions, clusters, or small molecules inside, resulting in stable compounds with unusual structures and electronic properties. These compounds are collectively defined as endohedral fullerenes. The most studied endohedral fullerenes are those containing metal atoms or ions inside, and these are referred to as endohedral metallofullerenes (EMFs). For EMFs, the inner isolated space of the fullerene cages can lead to the stabilization of unique clusters, which are otherwise not synthetically accessible. This offers an excellent environment and opportunity for investigating the nature of previously unobserved metal–metal, metal–non-metal, and metal–fullerene interactions, which are of fundamental interest and importance. Up until now, most of the work in this field has been mainly focused on the rare-earth metals and related elements (groups II, III, and IV). The encapsulation of other elements of the periodic table could potentially lead to totally new structures and bonding motifs and to material properties beyond those of the existing EMFs. Actinides were originally explored as encapsulated elements in fullerenes when Smalley et al. (Science19922571661) reported mass spectral evidence of actinide endohedral fullerenes back in 1992. However, the full characterization of these actinide endohedral fullerenes, including single crystal X-ray diffractometric analyses, was not reported until very recently, in 2017. In this Account, we highlight some recent advances made in the field of EMF compounds, focusing primarily on the molecular and electronic structures of novel actinide-based EMFs, new evidence for the formation mechanisms of EMFs, and the influence of the entrapped species on the reactivity and regiochemistry of EMF compounds. We recently reported that some monometallic actinide EMFs represent the first examples of tetravalent metals encapsulated inside fullerenes that exhibit considerably stronger host–guest interactions when compared to those observed for the lanthanide EMFs. These unusually strong metal–cage interactions, along with very high mobilities of the actinides inside the fullerene cages at high temperatures, result in the stabilization of unexpected non-IPR (isolated pentagon rule) fullerene cages encapsulating only one metal ion. Strikingly, such covalent stabilization factors had never been previously observed, although Sm@C 2v (19138)-C76 was the first reported mono-EMF with a non-IPR cage, see details below. In addition, we showed that a long sought-after actinide–actinide bond was obtained upon encapsulation of U2 inside an I h (7)-C80 fullerene cage. More interestingly, we demonstrated that actinide multiple bonds, which are very difficult to prepare by conventional synthetic methods, are stabilized when trapped inside fullerene cages. A totally unexpected and previously unreported uranium carbide cluster, UCU, was fully characterized inside an EMF, U2C@I h (7)-C80, which, for the first time, clearly exhibits two unsu...

Successful isolation and unambiguous crystallographic assignment of a series of higher carbide cluster metallofullerenes present new insights into the molecular structures and cluster-cage interactions of endohedral metallofullerenes. These new species are identified as LaC@C(41)-C, LaC@D(85)-C, LaC@C(132)-C, LaC@C(157)-C, and LaC@C(175)-C. This is the first report for these new cage structures except for D(85)-C. Our experimental and theoretical results demonstrate that LaC are more inclined to exist stably in the carbide form LaC@C rather than as the dimetallofullerenes La@C, which are rationalized by considering a synergistic effect of inserting a C unit into the cage, which ensures strong metal-cage interactions by partially neutralizing the charges from the metal ions and by fulfilling the coordination requirement of the La ions as much as possible.