- Lu2@C2n (2n = 82, 84, 86): Crystallographic Evidence of Direct Lu-Lu Bonding between Two Divalent Lutetium Ions Inside Fullerene Cages
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Although most of the M2C2n-type metallofullerenes (EMFs) tend to form carbide cluster EMFs, we report herein that Lu-containing EMFs Lu2C2n (2n = 82, 84, 86) are actually dimetallofullerenes (di-EMFs), namely, Lu2@Cs(6)-C82, Lu2@C3v(8)-C82, Lu2@D2d(23)-C84, and Lu2@C2v(9)-C86. Unambiguous X-ray results demonstrate the formation of a Lu-Lu single bond between two lutetium ions which transfers four electrons in total to the fullerene cages, thus resulting in a formal divalent state for each Lu ion. Population analysis indicates that each Lu atom formally donates a 5d electron and a 6s electron to the cage with the remaining 6s electron shared with the other Lu atom to form a Lu-Lu single bond so that only four electrons are transferred to the fullerene cages with the formal divalent valence for each lutetium ion. Accordingly, we confirmed both experimentally and theoretically that the dominating formation of di-EMFs is thermodynamically very favorable for Lu2C2n isomers.
- Shen, Wangqiang,Bao, Lipiao,Wu, Yongbo,Pan, Changwang,Zhao, Shasha,Fang, Hongyun,Xie, Yunpeng,Jin, Peng,Peng, Ping,Li, Fang-Fang,Lu, Xing
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supporting information
p. 9979 - 9984
(2017/08/02)
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- Incarceration of Higher-Order Fullerenes within Cyclotriveratrylene-Based Hemicarcerands Allows Selective Isolation of C76, C78, and C84from a Commercial Fullerene Mixture
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Size-complementary cyclotriveratrylene (CTV)-based hosts can incarcerate C76, C78, and C84, thus allowing the selective isolation of these higher-order fullerenes from a commercially available mixture of fullerenes. The hemicarceplexes, formed after the encapsulation of the size-complementary fullerenes within the hosts, are isolated by column chromatography and released at elevated temperature, thereby leading to the isolation of C76/C78and C84in good purities (up to 95 and 88 %, respectively).
- Liu, Kuang-Shun,Li, Ming-Jhe,Lai, Chien-Chen,Chiu, Sheng-Hsien
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supporting information
p. 17468 - 17476
(2016/11/23)
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- An epilogue on the C78-fullerene family: The discovery and characterization of an elusive isomer
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(Figure Presented) Missing relative found: The last representative of the first multi membered fullerene family, C78(4), has been synthesized and isolated. Its connectivity pattern was confirmed by a single-crystal X-ray analysis of its chlorinated derivative C78(4)Cl18 (see picture). The crystal structure also reveals the presence of unusual, short intermolecular chlorine contacts.
- Simeonov, Kalin S.,Amsharov, Konstantin Yu.,Krokos, Evangelos,Jansen, Martin
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p. 6283 - 6285
(2009/04/07)
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- Synthesis and X-ray or NMR/DFT structure elucidation of twenty-one new trifluoromethyl derivatives of soluble cage isomers of C76, C 78, C84, and C90
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Adding 1% of the metallic elements cerium, lanthanum, and yttrium to graphite rod electrodes resulted in different amounts of the hollow higher fullerenes (HHFs) C76-D2(1), C78-C 2v(2), and C78-C2v(3) in carbon-arc fullerene-containing soots. The reaction of trifluoroiodomethane with these and other soluble HHFs at 520-550°C produced 21 new C 76,78,84,90(CF3)n derivatives (n = 6, 8, 10, 12, 14). The reaction with C76-D2(1) produced an abundant isomer of C2-(C76-D2(I))(CF3) 10 plus smaller amounts of an isomer of C1-(C 76-D2(1))(CF3)6, two isomers of C1-(C76-D2(I))(CF3)8, four isomers of C1-(C76-D2(1))(CF 3)10, and one isomer of C2-(C 76-D2(1))(CF3)12. The reaction with a mixture of C78-D3(1), C78-C2v(2), and C78-C2v(3) produced the previously reported isomer C1-(C78-C2v(3))(CF3)12 (characterized by X-ray crystallography in this work) and the following new compounds: C2-(C78-C2v(3)(CF3) 8, C2-(C78-D3(1))(CF 3)10 and Cs-(C78-C 2v(2)(CF3)10 (both characterized by X-ray crystallography in this work); C2-(C78-C 2v(2)(CF3)10; and C1-C 78(CF3)14 (cage isomer unknown). The reaction of a mixture of soluble higher fullerenes including C84 and C 90 produced the new compounds C1-C84(CF 3)10 (cage isomer unknown), C1-(C 84-C2(11))(CF3)12 (X-ray structure reported recently), D2-(C84-D2(22))(CF 3)12, C1-C84-D2(22)) (CF3)12, C1-C84(CF3) 14 (cage isomer unknown), C1-C90-C 1(32))(CF3)12, and another isomer of C 1-C90(CF3)12 (cage isomer unknown). All compounds were studied by mass spectrometry, 19F NMR spectroscopy, and DFT calculations. An analysis of the addition patterns of these compounds and three other HHF(X)n compounds with bulky X groups has led to the discovery of the following addition-pattern principle for HHFs: In general, the most pyramidal cage C(sp2) atoms in the parent HHF, which form the most electron-rich and therefore the most reactive cage C-C bonds as far as 1,2-additions are concerned, are not the cage C atoms to which bulky substituents are added. Instead, ribbons of edge-sharing p-C6(X) 2 hexagons, with X groups on less pyramidal cage C atoms, are formed, and the otherwise most reactive fullerene double bonds remain intact.
- Kareev, Ivan E.,Popov, Alexey A.,Kuvychko, Igor V.,Shustova, Natalia B.,Lebedkin, Sergey F.,Bubnov, Vyachevslav P.,Anderson, Oren P.,Seppelt, Konrad,Strauss, Steven H.,Boltalina, Olga V.
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p. 13471 - 13489
(2009/02/06)
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- Single-stage plasma-arc synthesis of metallo-endofullerences
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Single-stage plasma-arc synthesis of metallo-endofullerences of the types C60Pd, C60Ni, and C60Cr, whose content in a mixture of extracted fullerenes was 0.05 to 0.15 wt %, was performed. The effect of introduction of these metals into the reaction plasma on the total yield of fullerenes and on the fraction composition of the fullerene mixture was studied. The fullerene mixtures were analyzed by mass spectrometry and liquid chromatography.
- Gerasimov,Kalinin,Nikonov,Titovets,Kalabushkin,Alekhin,Nekrasov,Rusetskaya,Arapov,Alekseev,Kustova,Lishchuk,Pleshkov,Semenov,Keskinov,Charykov
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p. 1888 - 1893
(2008/04/05)
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- Synthesis of endohedral di-and monometallofullerenes Y2@C 84, Ce2@C78, and M@C82 (M = Y, Ce)
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Endohedral metallofullerenes Y2@C84, Ce 2@C78, and M@C82 (M = Y, Ce) were synthesized by the electric arc method and isolated from the soot using extraction with o-dichlorobenzene. Pure (98%) endohedr
- Kareev,Bubnov,Yagubskii
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p. 2140 - 2144
(2008/09/19)
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- Production, isolation and structural characterization of [92]fullerene isomers
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High-resolution 13C NMR has been used to structurally characterize a single isomer possessing C2 molecular sym)metry as well as an inseparable mixture of other isomers of [92]fullerene, produced from dysprosium arc-burned soot, separ
- Tagmatarchis, Nikos,Arcon, Denis,Prato, Maurizio,Shinohara, Hisanori
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p. 2992 - 2993
(2007/10/03)
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- A catalytic synthesis and structural characterization of a new [84]fullerene isomer
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The synthesis, separation and isolation of a new [84]fullerene isomer from arc-burned soot of dysprosium-doped graphite composite rods is reported; high-resolution 13C NMR and electronic absorption UV-VIS-NIR spectroscopy were used to characterize this material, which was found to possess C2 molecular symmetry; the successful synthesis of the new [84-C2]fullerene isomer can be ascribed to a catalytic role played by the doped Dy metal atoms in the composite rods.
- Tagmatarchis,Okada,Tomiyama,Yoshida,Kobayashi,Shinohara
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p. 1366 - 1367
(2007/10/03)
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- Isolation and crystallographic characterization of ErSc2N@C80: An endohedral fullerene which crystallizes with remarkable internal order
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The ErnSc3-nN@C80 (n = 0-3) family of four endohedral fullerenes has been prepared by vaporization of graphite rods packed with 2% Sc2O3/3% Er2O3/95% graphite powder in a Kraetschmer-Huffman fullerene generator under dynamic flow of helium and dinitrogen. ErSc2N@C80 has been isolated in pure form via three stages of high-pressure liquid chromatography and characterized by mass spectrometry. The first structure of a mixed metal endohedral, ErSc2N@C80, has been determined by single-crystal X-ray diffraction at 90 K on ErSc2N@C80·CoII(OEP)·1.5C 6H6·0.3CHCl3, which was obtained by diffusion of a solution of ErSc2N@C80 in benzene into a solution of CoII(OEP) (OEP is the dianion of octaethylporphyrin) in chloroform. The structure of ErSc2N@C80 consists of a planar ErSc2N unit surrounded by an icosahedral C80 cage. The nominal Er-N distance is 2.089(9) A and the Sc-N distance is, as expected, shorter, 1.968(6) A. Despite its location within the C80 cage, the ErSc2N unit displays a remarkable degree of order within the solid-state structure. The metal ions make close contact with individual carbon atoms of the cage with shortest Sc-C distances, in the range of 2.03-2.12 A, and shortest Er-C distances of 2.20 and 2.22 A. Two different, but equally populated, orientations of the Ih C80 cage were required to describe the fullerene portion of the structure. Although these C80 cages are located on a crystallographic mirror plane, that plane does not coincide with a mirror plane of the cages themselves. Consequently, the cage is disordered over four superimposed sites.
- Olmstead,De Bettencourt-Dias,Duchamp,Stevenson,Dorn,Balch
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p. 12220 - 12226
(2007/10/03)
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- Production of fullerenes and single-wall carbon nanotubes by high-temperature pulsed arc discharge
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Fullerenes and single-wall carbon nanotubes (SWNTs) have been produced for the first time by the high-temperature pulsed arc-discharge technique, which has developed in this laboratory. Fullerenes are identified quantitatively by high-performance liquid chromatography (HPLC), and scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations reveal a significant amount of production of bundles of SWNTs in soot. The pulse arc production of fullerenes and SWNTs favors the high-temperature (≥ 1000°C), long pulses (≥ 1 ms) and a heavy rare gas such as Ar or Kr as a buffer gas. We have found that fullerenes and SWNTs have complementary relationships in their early stage of production. The details of the pulsed arc discharge have been obtained by observing the transition from the pulsed arc discharge to the steady arc discharge while increasing the pulse width.
- Sugai, Toshiki,Omote, Hideki,Bandow, Shunji,Tanaka, Nobuo,Shinohara, Hisanori
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p. 6000 - 6005
(2007/10/03)
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