A diuranium carbide cluster stabilized inside a C80 fullerene cage

Zhang, Xingxing; Li, Wanlu; Feng, Lai; Chen, Xin; Hansen, Andreas; Grimme, Stefan; Fortier, Skye; Sergentu, Dumitru‐Claudiu; Duignan, Thomas J.; Autschbach, Jochen; Wang, Shuao; Wang, Yaofeng; Velkos, Georgios; Popov, Alexey A.; Aghdassi, Nabi; Duhm, Steffen; Xiao-hong, LI; Li, Jun; Echegoyen, Luís; Schwarz, W. H. Eugen; Chen, Ning

doi:10.1038/s41467-018-05210-8

Cited by 67 publications

(122 citation statements)

References 68 publications

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“…Given that its UV/Vis spectrum is similar to those endohedral metallofullerenes possessing aC 80 -I h cage and by analogy with Lu 2 TiC@I h -C 80 ,r eported by Popov and co-workers, [2] the internal cluster was assumed to be Sc 2 CU which has aplanar structure.A se xpected, the oxidation state of Ui s4+ and therefore there is aformal electron transfer between host and guest of six electrons.N ote that the UÀCb ond length is computed to be 2.070 ,avery short distance essentially identical to the X-ray bond length found very recently for ad iuranium carbide cluster (U = C = U) stabilized inside C 80 (2.03 ). [13] Thea nalysis of the highest occupied orbitals for Sc 2 CU@I h -C 80 corroborates that there is ad ouble bond between Ua nd C ( Figure 6a nd Figure S12). TheU -C distance is comparable to those found for uranium methylidene complexes H 2 C = UHX (X = F, Cl and Br) [14] and longer than those found for uranium methylidyne molecules HC UX 3 (X = F, Cl and Br) with CUt riple bonds (1.90-1.94 , see also Table S2).…”

Section: Angewandte Chemiementioning

confidence: 57%

Purification of Uranium‐based Endohedral Metallofullerenes (EMFs) by Selective Supramolecular Encapsulation and Release

et al. 2018

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Supramolecular nanocapsule 1⋅(BArF) is able to sequentially and selectively entrap recently discovered U @C and unprecedented Sc CU@C , simply by soaking crystals of 1⋅(BArF) in a toluene solution of arc-produced soot. These species, selectively and stepwise absorbed by 1⋅(BArF) , are easily released, obtaining highly pure fractions of U @C and Sc CU@C in one step. Sc CU@C represents the first example of a mixed metal actinide-based endohedral metallofullerene (EMF). Remarkably, the host-guest studies revealed that 1⋅(BArF) is able to discriminate EMFs with the same carbon cage but with different encapsulated cluster and computational studies provide support for these observations.

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Section: Angewandte Chemiementioning

confidence: 57%

Purification of Uranium‐based Endohedral Metallofullerenes (EMFs) by Selective Supramolecular Encapsulation and Release

et al. 2018

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“…A new member of CCMFs, namely U 2 C@ I h (7)‐C 80 , has also been unambiguously identified recently by single‐crystal XRD (Figure a). The U atoms in the UCU unit exhibit a +5 valence state based on the quantum‐chemistry results, which is different from that in mono‐uranium EMFs, such as U@ D 3 h (1)‐C 74 , U@ C 1 (17418)‐C 76 , U@ C 1 (28324)‐C 80 , U@ C 2 (5)‐C 82 , and U@ C 2 v (9)‐C 82 .…”

Section: Carbide Clusterfullerenesmentioning

confidence: 74%

“…Very recently, Chen and co‐workers reported the synthesis and structural characterization of two other novel uranium‐containing CCMFs, U 2 C 2 @I h (7)‐C 80 and U 2 C 2 @ D 3 h (5)‐C 78 . Surprisingly, each U atom takes a different oxidation state (U 4+ ) in the U 2 C 2 clusters, which are different from that of the previously reported U 2 C@ I h (7)‐C 80 (U 5+ ), thus resulting in six electrons being transferred from the U 2 C 2 cluster to the corresponding I h (7)‐C 80 and D 3 h (5)‐C 78 cages.…”

Section: Carbide Clusterfullerenesmentioning

confidence: 88%

Endohedral Metallofullerenes: New Structures and Unseen Phenomena

Shen

2020

Chemistry A European J

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Endohedral metallofullerenes (EMFs), namely fullerenes with metallic species encapsulated inside, represent an ideal platform to investigate metal–metal or metal–carbon interactions at the sub‐nanometer scale by means of single‐crystal X‐ray diffraction (XRD) crystallography. Herein, recent progress in the identification of new structures and unprecedented properties are discussed according to the categories of monometallofullerenes, dimetallofullerenes, carbide clusterfullerenes, and nitride clusterfullerenes. In particular, the dimerization and the cage‐isomer dependent oxidation state of the inner metal atom are summarized in terms of pristine monometallofullerenes. Metal–metal bonds involving lanthanide–lanthanides or actinide–actinides are discussed based on both experimental and theoretical studies. The cluster–cage matching and/or mutual selections, as well as the rarely seen M=C double bonds, are discovered in M2C2@C2n, U2C@C80, M2TiC@C80, and Ti3C3@C80. Subsequently, the geometries of different M3N clusters in various cages are discussed, revealing size‐matching between the internal M3N cluster and the outer cage induced by the planarity of the cluster. Finally, an outlook regarding the future developments of the molecular structures and applications of EMFs is presented.

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“…Incorporation of reactive gases induces the formation of di-uranium EMFs U 2 C 78 , U 2 C 79, U 2 @I h (7)-C 80 [24] , and UCU@I h (7)-C 80 . [25] Having made these observations, we turned our attention towards the synthesis and extraction of smaller uranofullerenes. To afford the latter, the synthetic experimental procedure and the extraction approach were modified.…”

Section: Preparation Of Emfsmentioning

confidence: 99%

Small Cage Uranofullerenes: 27 Years after Their First Observation

Gómez‐Torres

Esper

Dunk

et al. 2019

Helvetica Chimica Acta

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The tetravalently stabilized fullerene cage of C28 is historically the most elusive small fullerene cage observed by employing the laser vaporization synthesis methodology. Its first observation reported by Smalley et al. in 1992 suggests that C28 is potentially the smallest and most stable fullerene ever observed. By using the Krätschmer−Huffman arc discharge synthesis method, we have recently succeeded in synthesizing a series of uranium‐endohedral fullerenes which differ from those reported by Smalley and co‐workers. Intrigued by this interesting mismatch, we tuned our experimental conditions to favor the formation and detection of these missing species. Experiments done using solvents of varying polarity allowed the observation of several empty and uranofullerenes. Extractions with pyridine and o‐DCB allowed for observation of small U@C2n (2n=28, 60, 66, 68, 70) by high resolution Fourier‐Transform Ion Cyclotron Resonance Mass Spectrometry (FT‐ICR MS). This is the first time that U@C28 is observed in soot produced by the Krätschmer‐Huffman arc‐discharge methodology. Carbon cage selection and spin density distribution on the endohedral metallofullerenes (EMFs) U@C60, U@C70, and U@C72 were studied by means of density functional theory (DFT) calculations. A plausible pathway for the formation of U@D3h‐C74 from U@D5h‐C70 through two C2 insertions and one Stone‐Wales rearrangement is proposed.

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A diuranium carbide cluster stabilized inside a C80 fullerene cage

Cited by 67 publications

References 68 publications

Purification of Uranium‐based Endohedral Metallofullerenes (EMFs) by Selective Supramolecular Encapsulation and Release

Purification of Uranium‐based Endohedral Metallofullerenes (EMFs) by Selective Supramolecular Encapsulation and Release

Endohedral Metallofullerenes: New Structures and Unseen Phenomena

Small Cage Uranofullerenes: 27 Years after Their First Observation

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