- Cage-Expansion of Fullerenes
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Despite the first proposal on the cage inflation of fullerenes in 1991, the chemical expansion of fullerenes has been still a formidable challenge. Herein, we provide an efficient methodology to expand [60] and [70]fullerene cages by the inclusion of totally C5N unit, giving nitrogen-containing closed structures as C65N and C75N with double fused heptagons. This method consists of two steps commenced with the construction of an opening by the reaction with triazine as a C3N source, followed by the cage reformation using N-phenylmaleimide as a C2 source. We also synthesized endohedral cages, demonstrating that the encapsulated H2O molecule inside the C75N cage prefers the orientation which maximizes the intramolecular interaction with the carbon wall. Additionally, we revealed the existence of a through-space magnetic dipolar interaction between the encapsulated H2 molecule and the embedded N atom.
- Zhang, Sheng,Hashikawa, Yoshifumi,Murata, Yasujiro
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supporting information
p. 12450 - 12454
(2021/08/20)
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- Stereoselective synthesis of amino-substituted cyclopentafullerenes promoted by magnesium perchlorate/ferric perchlorate
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A facile one-step reaction of [60]fullerene with cinnamaldehydes and amines promoted by magnesium perchlorate/ferric perchlorate under air conditions afforded a series of rare amino-substituted cyclopentafullerenes in moderate to good yields. Stereoselectivity was readily achieved. Secondary amines exclusively produced N,N-disubstituted cyclopentafullerenes as cis isomers, while arylamines gave N-monosubstituted cyclopentafullerenes with a preference of cis isomers as major products. N-Monosubstituted cyclopentafullerenes could be further converted into other scarce cyclopentafullerenes in the presence of acid chloride or paraformaldehyde. A possible reaction pathway was proposed to elucidate the formation of amino-substituted cyclopentafullerenes.
- Ma, Wan,Wang, Kun,Huang, Cheng,Wang, Hui-Juan,Li, Fa-Bao,Sun, Rui,Liu, Li,Liu, Chao-Yang,Asiri, Abdullah M.
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supporting information
p. 964 - 974
(2020/02/15)
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- Lewis base-catalyzed double nucleophilic substitution reaction of N-tosylaziridinofullerene with thioureas or guanidines
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Lewis base-catalyzed double nucleophilic substitution reaction of N-tosylaziridinofullerene with thioureas or guanidines affords the fullerothiazolidin-2-imine or fulleroimidazolidin-2-imine derivatives, respectively. In the case of unsymmetrical thiourea
- Meng, Qi,Cheng, Jun-Yu,Miao, Chun-Bao,Sun, Xiao-Qiang,Yang, Hai-Tao
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p. 2566 - 2570
(2017/06/13)
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- DMAP-Mediated Synthesis of Fulleropyrrolines: Reaction of [60]Fullerene with Aromatic Aldehydes and Arylmethanamines in the Absence or Presence of Manganese(III) Acetate
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A series of scarce fulleropyrrolines were synthesized via DMAP-mediated one-step reaction of [60]fullerene with commercially inexpensive aromatic aldehydes and arylmethanamines in the absence or presence of manganese(III) acetate. In the case of aminodiphenylmethane, novel 2,5,5-trisubstituted fulleropyrrolines could be easily obtained without the addition of manganese(III) acetate. As for arylmethanamines without α-substitutions, the addition of manganese(III) acetate was required to suppress the formation of fulleropyrrolidines, in order to generate the desired 2,5-disubstituted fulleropyrrolines. Two tautomers were produced as expected when different aryl groups (Ar1 ≥ Ar2) from aromatic aldehydes and arylmethanamines were employed in the synthesis. A plausible reaction mechanism for the formation of fulleropyrrolines is proposed.
- Peng, Jie,Xiang, Jun-Jun,Wang, Hui-Juan,Li, Fa-Bao,Huang, Yong-Shun,Liu, Li,Liu, Chao-Yang,Asiri, Abdullah M.,Alamry, Khalid A.
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p. 9751 - 9764
(2017/09/22)
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- 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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- CF2-Bridged C60 Fullerene Dimers and their Optical Transitions
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Fullerene dyads bridged with perfluorinated linking groups have been synthesized through a modified arc-discharge procedure. The addition of Teflon inside an arc-discharge reactor leads to the formation of dyads, consisting of two C60 fullerenes bridged by CF2 groups. The incorporation of bridging groups containing electronegative atoms lead to different energy levels and to new features in the photoluminescence spectrum. A suppression of the singlet oxygen photosensitization indicated that the radiative decay from singlet-to-singlet state is favoured against the intersystem crossing singlet-to-triplet transition.
- Dallas, Panagiotis,Zhou, Shen,Cornes, Stuart,Niwa, Hiroyuki,Nakanishi, Yusuke,Kino, Yasuhiro,Puchtler, Tim,Taylor, Robert A.,Briggs, G. Andrew. D.,Shinohara, Hisanori,Porfyrakis, Kyriakos
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p. 3540 - 3543
(2017/11/22)
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- Cu-catalyzed C-H amination of Hydrofullerenes leading to 1,4-Difunctionalized Fullerenes
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A novel and highly efficient Cu-catalyzed C-H amination of the monofunctionalized hydrofullerenes for the synthesis of 1,4-difunctional fullerenes has been reported. A new series of 1,4-fullerene derivatives having various monoamine addends were synthesized in good to high yields under mild reaction conditions. The controlled experiments revealed that the reaction proceeds through the formation of a fullerene monoradical as a key intermediate followed by coupling with an amine radical.
- Si, Weili,Lu, Shirong,Bao, Ming,Asao, Naoki,Yamamoto, Yoshinori,Jin, Tienan
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supporting information
p. 620 - 623
(2014/04/03)
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- Method for the synthesis of amine-functionalized fullerenes involving set-promoted photoaddition reactions of -silylamines
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A novel method for the preparation of structurally diverse fullerene derivatives, which relies on the use of single electron transfer (SET)-promoted photochemical reactions between fullerene C60 and α-trimethylsilylamines, has been developed. Photoirradiation of 10% EtOH-toluene solutions containing C60 and α-silylamines leads to high-yielding, regioselective formation of 1,2-adducts that arise through a pathway in which sequential SET-desilylation occurs to generate α-amino and C60 anion radical pair intermediates, which undergo C-C bond formation. Protonation of generated α-aminofullerene anions gives rise to formation of monoaddition products that possess functionalized α-aminomethyl-substituted 1,2-dihydrofullerene structures. Observations made in this effort show that the use of EtOH in the solvent mixture is critical for efficient photoproduct formation. In contrast to typical thermal and photochemical strategies devised previously for the preparation of fullerene derivatives, the new photochemical approach takes place under mild conditions and does not require the use of excess amounts of substrates. Thus, the method developed in this study could broaden the scope of fullerene chemistry by providing a simple photochemical strategy for large-scale preparation of highly substituted fullerene derivatives. Finally, the α-aminomethyl-substituted 1,2-dihydrofullerene photoadducts are observed to undergo photoinduced fragmentation reactions to produce C60 and the corresponding N-methylamines.
- Lim, Suk Hyun,Yi, Jinju,Moon, Gyeong Min,Ra, Choon Sup,Nahm, Keepyung,Cho, Dae Won,Kim, Kyungmok,Hyung, Tae Gyung,Yoon, Ung Chan,Lee, Ga Ye,Kim, Soojin,Kim, Jinheung,Mariano, Patrick S.
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supporting information
p. 6946 - 6958
(2014/08/18)
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- Modification of fulleropyrazolines modulates their cleavage by light
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The extraordinary electrochemistry and the tunability of their energy levels allows the use of fulleropyrazolines in photovoltaics and charge-transfer systems. Here we show that substitution in position 1 tunes photolytic stability; electron-donating groups facilitate 1,3-dipolar cycloreversion to fullerene. This discovery has implications not only for photovoltaic stability but also highlights a potential strategy for photo-controlled fullerene release systems ('photo-caged'/'photo-activated' fullerene). This journal is
- Rutte, Reida N.,Parsons, Thomas B.,Davis, Benjamin G.
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supporting information
p. 12297 - 12299
(2015/02/19)
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- Facile catch and release of fullerenes using a photoresponsive molecular tube
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A novel M2L2 molecular tube capable of binding fullerene C60 was synthesized from bispyridine ligands with embedded anthracene panels and Ag(I) hinges. Unlike previous molecular cages and capsules, this open-ended tubular host can accommodate a single molecule of various C60 derivatives with large substituents. The fullerene guest can then be released by using the ideal, noninvasive external stimulus, light.
- Kishi, Norifumi,Akita, Munetaka,Kamiya, Motoshi,Hayashi, Shigehiko,Hsu, Hsiu-Fu,Yoshizawa, Michito
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p. 12976 - 12979
(2013/09/24)
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- A Series of inorganic solid nitrogen sources for the synthesis of metal nitride clusterfullerenes: The dependence of production yield on the oxidation state of nitrogen and counter ion
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A series of nitrogen-containing inorganic solid compounds with variable oxidation states of nitrogen and counter ions have been successfully applied as new inorganic solid nitrogen sources toward the synthesis of Sc-based metal nitride clusterfullerenes (Sc-NCFs), including ammonium salts [(NH 4)xH3-xPO4 (x = 0-2), (NH 4)2SO4, (NH4)2CO 3, NH4X (X = F, Cl), NH4SCN], thiocyanate (KSCN), nitrates (Cu(NO3)2, NaNO3), and nitrite (NaNO2). Among them, ammonium phosphates ((NH4) xH3-xPO4, x = 1-3) and ammonium thiocyanate (NH4SCN) are revealed to behave as better nitrogen sources than others, and the highest yield of Sc-NCFs is achieved when NH4SCN was used as a nitrogen source. The optimum molar ratio of Sc2O 3:(NH4)3PO4·3H2O: C and Sc2O3:NH4SCN:C has been determined to be 1:2:15 and 1:3:15, respectively. The thermal decomposition products of these 12 inorganic compounds have been discussed in order to understand their different performances toward the synthesis of Sc-NCFs, and accordingly the dependence of the production yield of Sc-NCFs on the oxidation state of nitrogen and counter ion is interpreted. The yield of Sc3N@C80 (Ih + D5h) per gram Sc2O3 by using the N 2-based group of nitrogen sources (thiocyanate, nitrates, and nitrite) is overall much lower than those by using gaseous N2 and NH4SCN, indicating the strong dependence of the yield of Sc-NCFs on the oxidation state of nitrogen, which is attributed to the in-situ redox reaction taking place for the N2-based group of nitrogen sources during discharging. For NH3-based group of nitrogen sources (ammonium salts) which exhibits a (-3) oxidation states of nitrogen, their performance as nitrogen sources is found to be sensitively dependent on the anion, and this is understood by considering their difference on the thermal stability and/or decomposition rate. Contrarily, for the N2-based group of nitrogen sources, the formation of Sc-NCFs is independent to both the oxidation state of nitrogen (+3 or +5) and the cation.
- Liu, Fupin,Guan, Jian,Wei, Tao,Wang, Song,Jiao, Mingzhi,Yang, Shangfeng
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supporting information
p. 3814 - 3822
(2013/05/09)
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- SEMICONDUCTING THIN [60]FULLERENE FILMS AND THEIR USE
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?The present invention relates to the use of soluble pentakis(alkylthio)derivatives of [60] fullerene as precursors for semiconducting thin [60] fullerene films by thermal decomposition and organic electronic devices using these films.
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Page/Page column 12; 13
(2013/07/25)
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- PCy3-catalyzed ring expansion of aziridinofullerenes with CO2 and aryl isocyanates: Evidence for a two consecutive nucleophilic substitution pathway on the fullerene cage
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A PCy3-catalyzed ring-expansion reaction of aziridine-fused fullerenes (aziridinofullerenes) through the insertion of CO2 and aryl isocyanates is disclosed. The reaction allows for CO2 fixation by aziridinofullerenes, producing oxazolidinone-fused fullerenes (oxazolidinofullerenes) in high yields, whereas treatment with aryl isocyanates led to a new fullerene family - imidazolidinone-fused fullerenes (imidazolidinofullerenes) - in good to high yields. Furthermore, a mechanistically related unprecedented fullerenyl phosphonium salt was successfully isolated. Using the isolated salt, mechanistic studies were also investigated. New balls please: A PCy3-catalyzed ring-expansion reaction of aziridine-fused fullerenes (aziridinofullerenes) by the insertion of CO2 and aryl isocyanates is disclosed (see scheme). This allows for CO2 fixation by aziridinofullerenes. The expansion with aryl isocyanates led to a new fullerene family, imidazolidinone-fused fullerenes, in high yields. A mechanistically related unprecedented fullerenyl phosphonium salt was also successfully isolated (Cy=cyclohexyl). Copyright
- Takeda, Youhei,Kawai, Hajime,Minakata, Satoshi
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supporting information
p. 13479 - 13483
(2013/10/08)
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- The reaction of fullerene C60 with halogen azides
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Reaction of fullerene C60 and halogen azides (IN3, BrN3) gives 1-halo-2-azidofullerenes, whose structures were proved by NMR and IR spectroscopy, MALDI-TOF mass spectrometry, and by their chemical transformations.
- Dzhemilev, Usein M.,Tuktarov, Airat R.,Yarullin, Ildar R.,Akhmetov, Arslan R.
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p. 326 - 328
(2014/01/06)
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- Reprint of: Preparation and UV/visible spectra of fullerenes C60 and C70
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The preparation and isolation of pure fullerene-60 and fullerene-70 is described. The solution UV/visible absorption spectra of the two molecules are presented.
- Hare,Kroto,Taylor
-
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- [(μ-H)3Re3 (CO) 9 (ν2, ν2,ν2-Sc2C2@C 3v(8)-C82)]: Face-capping cluster complex of an endohedral fullerene
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Fullerenes with atoms, ions, or clusters in their inner space are referred to as endohedral fullerenes. These spherical molecules have unique properties that can be very different from those of the empty fullerenes.[1, 2] Among these hybrid molecules, end
- Chen, Chia-Hsiang,Yeh, Wen-Yann,Liu, Yi-Hung,Lee, Gene-Hsiang
-
supporting information
p. 13046 - 13049
(2013/03/13)
-
- Construction and photophysics study of supramolecular complexes composed of three-point binding fullerene-trispyridylporphyrin dyads and zinc porphyrin
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A series of novel supramolecular complexes composed of a three-point binding C60-trispyridylporphyrin dyad (1) or C70- trispyridylporphyrin dyad (2) and zinc tetraphenylporphyrin (ZnP) were constructed by adopting a covalent-coordinate bonding approach, composed of three-point binding. The dyads and self-assembled supramolecular triads or pentads formed by coordinating the pyridine groups located on the dyads to ZnP, have been characterized by means of spectral and electrochemical techniques. The formation constants of ZnP-1 and ZnP-2 complexes were calculated as 1.4 × 104 M-1 and 2.0 × 104 M-1, respectively, and the Stern-Volmer quenching constants K SV were founded to be 2.9 × 104 M-1 and 5.5 × 104 M-1, respectively, which are much higher than those of other supramolecular complexes such as previously reported ZnP-3 (N-ethyl-2-(4-pyridyl)-3,4-fulleropyrrolidine). The electrochemical investigations of these complexes suggest weak interactions between the constituents in the ground state. The excited states of the complexes were further monitored by time-resolved fluorescence measurements. The results revealed that the presence of the multiple binding point dyads (1 or 2) slightly accelerated the fluorescence decay of ZnP in o-DCB relative to that of the single-point bound supramolecular complex ZnP-3. In comparison with 1 and 2, C70 is suggested as a better electron acceptor relative to C60. DFT calculations on a model of supramolecular complex ZnP-1 (with one ZnP entity) were performed. The results revealed that the lowest unoccupied molecular orbital (LUMO) is mainly located on the fullerene cage, while the highest occupied molecular orbital (HOMO) is mainly located on the ZnP macrocycle ring, predicting the formation of radical ion pair ZnP +-H2P-C60- during photo-induced reaction.
- Xu, Wei,Feng, Lai,Wu, Yishi,Wang, Taishan,Wu, Jingyi,Xiang, Junfeng,Li, Bao,Jiang, Li,Shu, Chunying,Wang, Chunru
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p. 428 - 433
(2014/03/21)
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- Radical reaction of [60]fullerene with phosphorus compounds mediated by manganese(III) acetate
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Radical reaction of [60]fullerene with phosphonates or phosphine oxide mediated by manganese(III) acetate dihydrate in chlorobenzene under three different conditions afforded three different types of phosphorylated fullerenes: singly bonded fullerene dime
- Wang, Guan-Wu,Wang, Cong-Zhou,Zou, Jian-Ping
-
experimental part
p. 6088 - 6094
(2011/10/09)
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- Direct arc-discharge assisted synthesis of C60H 2(C3H5N): A cis-1-pyrrolino C60 fullerene hydride with unusual redox properties
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By direct arc synthesis of C60H2(C3H 5N) using a modified Kraetschmer-Huffman method, it is demonstrated for the first time that exohedral fullerenes with large side groups can be formed under the arc and reactive gas atmosphere conditions. The thus formed novel pyrrolino fullerene hydride was comprehensively characterized by UV-vis, infrared (IR), Raman and nuclear magnetic resonance (NMR) and studied by means of electrochemistry and in situ electron spin resonance/visible-near infrared (ESR/Vis-NIR) spectroelectrochemistry. The detailed NMR and absorption spectroscopic studies show C60H2(C3H 5N) as the fullerene hydride with a pyrrolino ring attached on the vicinal position of two hydrogen atoms. This first cycloaddition adduct of C60H2 gives rise to an unusual reversible dimerization of its anion radicals and a loss of cage hydrogen atoms at the third electron transfer. The spectroelectrochemical study confirms the formation of a [C 60H2(C3H5N)]- radical and the diamagnetic state of [C60H2(C3H 5N)] 2-. This study reveals a unique function of a carbide structure like Al4C3 and the presence of a reactive gas atmosphere with NH3 in the formation of such an exohedral pyrrolino structure C60H2(C3H5N).
- Chen, Ning,Klod, Sabrina,Rapta, Peter,Popov, Alexey A.,Dunsch, Lothar
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experimental part
p. 2608 - 2615
(2011/11/12)
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- Complexation and C-H/C-P bond activation of the (PPh2)C 60H molecule on triosmium carbonyl clusters
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Reaction of (PPh2)C60H (1) and Os3(CO) 10(NCMe)2 produces Os3(CO)10(μη 3-(PPh2)C60H) (2), with one edge of the triosmium cluster bridged by the phosphine gr
- Yeh, Wen-Yann,Tsai, Kune-You
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p. 604 - 609
(2010/04/25)
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- The thermodynamic properties of bis(n6-ethoxybenzene)chromium fulleride from T → 0 to 340 K
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The temperature dependence of the heat capacity of crystalline bis-(n6-ethoxybenzene)chro- mmm fulleride [(n6-(EtOPh))2Cr]-+[C 60]- was studied for the first time by adiabatic vacuum calorimetry over the temperature range 6-340 K with errors of ±0.2%. The temperature dependence of the EPR signal parameters of bi's-(n6-ethoxybenzene)chromium fulleride was studied for the first time from 120 to 340 K. A reversible endothermic transformation was observed between 160 and 250 K during heating; it was caused by the dissociation of the [(C60)2]2- dimer and the formation of the [(n6-(EtOPh))2Cr]+[C60]- fulleride; its standard thermodynamic characteristics were estimated and analyzed. The experimental data were used to calculate the standard thermodynamic functions, including the heat capacity, enthalpy, entropy, and Gibbs function of the fulleride dimer from T→ 0 to 160 K and the [(n6-(EtOPh))2Cr] +[C60] monomeric complex over the temperature range 250-340 K. The standard thermodynamic properties of the fulleride studied, fullerides studied earlier, and fullerite C60 were compared. Pleiades Publishing, Ltd., 2010.
- Ruchenin,Smirnova,Markin,Shevelev,Kuropatov,Lopatin,Domrachev,Markin
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p. 928 - 933
(2011/01/10)
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- Simple combustion production and characterization of octahydro[60]fullerene with a non-IPR C60 cage
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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 C60 cage (C60 isomer #1809C60) 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.
- Weng, Qun-Hong,He, Qiao,Liu, Ting,Huang, Hui-Ying,Chen, Jian-Hua,Gao, Zhi-Yong,Xie, Su-Yuan,Lu, Xin,Huang, Rong-Bin,Zheng, Lan-Sun
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p. 15093 - 15095
(2010/12/20)
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- Thermodynamics of the bis(η6-t-butylphenyl)chromium fulleride [Cr{η6-(t-BuPh)}2]?+C60 ?-
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In this work, the temperature dependence of heat capacity C p,mo = f(T) of crystalline bis(η6-t- butylphenyl)chromium fullende between T= 6 and 360K was measured for the first time by precision adiabatic vacuum calorimetry
- Ruchenin, Vitaly A.,Markin, Alexey V.,Smirnova, Natalia N.,Markin, Gennady V.,Shevelev, Yurii A.,Cherkasov, Vladimir K.,Kuropatov, Vyatcheslav A.,Ketkov, Sergey Y.,Lopatin, Mikhail A.,Domrachev, Georgy A.
-
-
- Synthesis of germanium encapsulated fullerene
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A method has been described for encapsulating Ge in a fullerene cage using GeO2 and a graphite composite rod as anode and graphite as cathode. Annealing in an inert atmosphere before arcing, and the amount of GeO2 in the rod determin
- Roy, Debmalya,Tripathi,Ram,Sathyamurthy
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p. 1244 - 1247
(2009/12/02)
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- One-step synthesis of fullerene hydride C60H2 via hydrolysis of acylated fullerenes
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(Figure Presented) The hitherto unexplored class of acylated fullerene compounds has been shown to be excellent C60H2 precursors. Upon a simple treatment with basic Al2O3, they are hydrolyzed quantitatively into
- Tzirakis, Manolis D.,Alberti, Mariza N.,Nye, Leanne C.,Drewello, Thomas,Orfanopoulos, Michael
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supporting information; experimental part
p. 5746 - 5749
(2009/12/26)
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- Palladium-catalyzed carbon-carbon bond formation and cleavage of organo(hydro)fullerenes
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Palladium-catalyzed reactions of organo-(hydro)fullerenes, new C-C bond formation, and cleaving processes for organo-(hydro)fullerenes were reported. These reactions caused the introduction of various organic fragments and a hydrogen atom to the fullerene
- Nambo, Masakazu,Itami, Kenichiro
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supporting information; experimental part
p. 4760 - 4764
(2009/12/26)
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- The thermodynamic properties of bis(η6-o-xylene)chromium(I) fulleride over the temperature range from T → 0 to 340 K
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The temperature dependence of the heat capacity of bis(η6-o- xylene)chromium(I) fulleride, [(η6-(o-xylene)) 2Cr]+?[C60]?-, over the temperature range 6-340 K was measured on an adiabatic va
- Markin,Ruchenin,Smirnova,Markin,Shevelev, Yu. A.,Kuropatov,Domrachev
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p. 1289 - 1294
(2010/03/04)
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- Metallofullerols and their Applications for Preparation of Medicine for Inhibition of Tumor Growth
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This invention provides a composition of polyhydroxylated metallofullerene compound and its application in the preparation of antitumor pharmaceutical. In one embodiment, metallofullerol comprising the formula, M@C2m(OH)x, wherein M is selected from rare earth elements such as La or Gd; m is carbon atoms of 41 or 30; x is a number of hydroxyl group of from 10 to about 50. Actually, due to the reset of the neighboring hydroxyl, the numbers of O and H in Carbon cage are different, formula are thus written as M@C2mOxHy. Comparing to the clinical anticancer drugs such as Paclitaxel, Cyclophosphamide, and Cisplatin, metallofullerol of M@C2m(OH)x or M@C2mOxHy has superior advantages of higher antitumor efficiency, low dosage, low toxicity, and better biocompatibility.
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Page/Page column 3
(2009/04/24)
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- Preparation and optical properties of fullerene/ferrocene hybrid hexagonal nanosheets and large-scale production of fullerene hexagonal nanosheets
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The supramolecular nanoarchitectures, C60/ferrocene nanosheets, were prepared by a simple liquid-liquid interfacial precipitation method and fully characterized by means of SEM, STEM, HRTEM, XRD, Raman and UV-vis-NIR spectra. The highly crystal
- Wakahara, Takatsugu,Sathish, Marappan,Miyazawa, Kun'ichi,Hu, Chunping,Tateyama, Yoshitaka,Nemoto, Yoshihiro,Sasaki, Toshio,Ito, Osamu
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p. 9940 - 9944
(2009/12/08)
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- Endohedral gadolinium-containing metallofullerenes in the trifluoromethylation reaction
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An efficient method for the synthesis of trifluoromethyl derivatives of endohedral gadolinium-containing metallofullerenes was proposed. High-purity (98-99%) trifluoromethyl derivatives Gd@C82(CF3) 5 (two isomers) and Gds
- Kareev,Bubnov,Yagubskii
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p. 1486 - 1491
(2009/09/30)
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- On the mechanism of the thermal retrocycloaddition of pyrrolidinofullerenes (retro-prato reaction)
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In contrast to N-methyl or N-unsubstituted pyrrolidinofullerenes, which efficiently undergo the retrocycloaddition reaction to quantitatively afford pristine fullerene, N-benzoyl derivatives do not give this reaction under the same experimental conditions. To unravel the mechanism of the retrocycloaddition process, trapping experiments of the in-situ thermally generated azomethine ylides, with an efficient dipolarophile were conducted. These experiments afforded the respective cycloadducts as an endolexo iso-meric mixture. Theoretical calculations carried out at the DFT level and by using the two-layered ONIOM (our own n-layered integrated molecular orbital and molecular mechanics) approach underpin the experimental findings and predict that the presence of the dienophile is not a basic requirement for the azomethine ylide to be able to leave the fullerene surface under thermal conditions. Once the 1,3-dipole is generated in the reaction medium, it is efficiently trapped by the dipolarophile (maleic anhydride or N-phenylmaleimide). However, for N-unsubstituted pyrrolidinofullerenes, the participation of the dipolarophile in assisting the 1,3-dipole to leave the fullerene surface throughout the whole reaction pathway is also a plausible mechanism that cannot be ruled out.
- Filippone, Salvatore,Barroso, Marta Izquierdo,Martin-Domenech, Angel,Osuna, Silvia,Sola, Miquel,Martin, Nazario
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supporting information; scheme or table
p. 5198 - 5206
(2009/05/27)
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- Oxidation of 3-alkyl-substituted 2-pyrazolino[60]fullerenes: A new formyl-containing building block for fullerene chemistry
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(Figure Presented) A new building block for fullerene chemistry, endowed with a formyl group on C-3 of the 2-pyrazoline ring, has been prepared in a simple two-step synthesis by oxidation of readily available 3-alkyl-substituted 2-pyrazolino[60]fullerenes; the new building block paves the way for the preparation of new light-harvesting fullerenes.
- Delgado, Juan Luis,Cardinali, Francois,Espildora, Eva,Torres, M. Rosario,Langa, Fernando,Martin, Nazario
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supporting information; experimental part
p. 3705 - 3708
(2009/07/09)
-
- Technology for manufacture of pure fullerenes C60, C 70 and a concentrate of higher fullerenes
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An integrated technology for manufacture of fullerenes was developed. It includes the following stages: synthesis of a fullerene black, extraction of a mixture of fullerenes from the black, preliminary separation of the mixture into concentrates enriched in C60 and C70 fullerenes, and production of C60 and C70 fullerenes of purity exceeding 99.5 and 98.0 wt %, respectively, from the concentrates.
- Grushko,Sedov,Shilin
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p. 448 - 455
(2008/02/03)
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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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- C48 buckybowl and C60 fullerene precursors on the basis of truxenone
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The synthesis of bromine-substituted truxenone derivatives which constitute prospective precursors of geodesic structures is presented. The underlying mechanism of fullerene formation from truxenone-based precursors during flash pyrolysis is discussed. Isolable quantities of C60 fullerene have been achieved by intramolecular condensation of a precursor containing all 60 carbon atoms in appropriate positions, 72 out of the 90 required C-C bonds, and 3 bromine atoms.
- Amsharov, Konstantin Yu.,Jansen, Martin
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p. 1497 - 1508
(2008/10/09)
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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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- Chemically Adjusting Plasma Temperature, Energy, and Reactivity (CAPTEAR) method using NOx and combustion for selective synthesis of Sc 3N@C80 metallic nitride fullerenes
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Goals are (1) to selectively synthesize metallic nitride fullerenes (MNFs) in lieu of empty-cage fullerenes (e.g., C60, C70) without compromising MNF yield and (2) to test our hypothesis that MNFs possess a different set of optimal formation parameters than empty-cage fullerenes. In this work, we introduce a novel approach for the selective synthesis of metallic nitride fullerenes. This new method is Chemically Adjusting Plasma Temperature, Energy, and Reactivity (CAPTEAR). The CAPTEAR approach with copper nitrate hydrate uses NOx vapor from NOx generating solid reagents, air, and combustion to tune the temperature, energy, and reactivity of the plasma environment. The extent of temperature, energy, and reactive environment is stoichiometrically varied until optimal conditions for selective MNF synthesis are achieved. Analysis of soot extracts indicate that percentages of C60 and Sc3N@C80 are inversely related, whereas the percentages of C70 and higher empty-cage C2n fullerenes are largely unaffected. Hence, there may be a competitive link in the formation and mechanism of C60 and Sc3N@C80. Using this CAPTEAR method, purified MNFs (96% Sc3N@C80, 12 mg) have been obtained in soot extracts without a significant penalty in milligram yield when compared to control soot extracts (4% Sc3N@C80, 13 mg of Sc3N@C 80). The CAPTEAR process with Cu(NO3)2· 2.5H2O uses an exothermic nitrate moiety to suppress empty-cage fullerene formation, whereas Cu functions as a catalyst additive to offset the reactive plasma environment and boost the Sc3N@C80 MNF production.
- Stevenson, Steven,Thompson, M. Corey,Coumbe, H. Louie,Mackey, Mary A.,Coumbe, Curtis E.,Phillips, J. Paige
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p. 16257 - 16262
(2008/09/17)
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- Synthesis of metallofullerenes by electric-arc method with a surface-modified electrode
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A method for synthesis of metallofullerenes by electric-arc sputtering of graphite, in which lanthanum compounds are deposited on the surface of a graphite electrode, was suggested. The influence exerted by the amount of deposited lanthanum on the yield of lanthanum was studied.
- Kuz'min,Borovkov,Kolker,Brazhyunas
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p. 559 - 564
(2007/10/03)
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- Magnetic moments of the endohedral cluster fullerenes Ho 3N@C80 and Tb3N@C80: The role of ligand fields
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(Figure Presented) Wait a moment: The strong ligand field within the M 3N cluster of the endohedral cluster fullerenes Ho 3N@C80 and Tb3N@C80 accounts for the unusual net magnetic moment of the compounds. As a result of these interactions the individual magnetic moments m of the metal ions (M = Ho or Tb) are not parallel or antiparallel to each other, but parallel to the M-N bond (see scheme).
- Wolf, Manfred,Mueller, Karl-Hartmut,Skourski, Yurii,Eckert, Dieter,Georgi, Petra,Krause, Matthias,Dunsch, Lothar
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p. 3306 - 3309
(2007/10/03)
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- Purification of endohedral trimetallic nitride fullerenes in a single, facile step
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A major hurdle hampering the development of fullerenes, endohedral metallofullerenes, and nanotubes has been the difficulty of obtaining high purity samples. Soots prepared in the usual manner via a Kraetschmer-Huffman electric-arc generator consist of mixtures of insoluble carbonaceous materials and soluble fullerenes: C60, C70, C76, C 78, C84, etc. When metals are introduced as endohedral species the complexity of the resultant soot is even greater because of the presence of multiple isomers of both the empty fullerenes and the endohedral metallofullerenes. Here, for the first time, we report that lanthanide trimetallic nitride endohedral metallofullerenes, A3N@C80 (A = lanthanide atom, e.g., Er, Gd, Ho, Lu, Sc, Tb, Tm, Y), can be obtained in pure form directly from as-prepared soots in a single facile step by taking advantage of their extraordinary kinetic chemical stability with respect to the other fullerenes in Diels-Alder reactions with a cyclopentadiene-functionalized resin. We show that careful control of conditions (stoichiometry, time, temperature) allows separation of fullerenes with different cage sizes, as well as isomeric species. Furthermore, the Diels-Alder reaction is thermally reversible, and we demonstrated that the bound empty-cage fullerenes and classical endohedral metallofullerenes can be recovered by displacement with maleic anhydride.
- Ge, Zhongxin,Duchamp, James C.,Cai, Ting,Gibson, Harry W.,Dorn, Harry C.
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p. 16292 - 16298
(2007/10/03)
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- A biphasic displacement of [60]fullerene from fac-(dihapto-[60]fullerene) (dihapto-1,10-phenanthroline) tricarbonyl molybdenum (0)
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The Lewis bases (=L) triphenylphosphine (PPh3) and tricyclohexyl phosphine (P(Cy)3) displace [60]fullerene (C60) from the complex fac-(η2-C60)(η2-phen)Mo(CO) 3 (phen = 1,10-phenanthroline). The progress of the reactions was followed observing the decrease of the absorbance values at 440 nm and by monitoring the stretching carbonyl region from 1700 to 2100 cm-1. The plots of absorbance vs. time were biexponential, indicative of a biphasic behavior, for reactions under flooding conditions where [L] ? [fac-(η2-C60)(η2-phen)Mo(CO) 3]. The plot of absorbance vs. time consisted of two consecutive segments: the first segment of the plot was a decrease of absorbance with time followed by a second segment where the absorbance increased with time. The first segment of the biphasic plot was ascribed to the solvent-assisted displacement of C60 from fac-(η2-C60)(η2- phen)Mo(CO)3 and the second segment to decomposition of the complex fac-(η1-L)(η2-phen)Mo(CO)3 produced in the first of the two consecutive reactions. The rate constant values corresponding to the first segment of the biphasic plot are independent of the chemical nature of L, the molar concentration of L, and the molar concentration of C60 but dependent on the chemical nature of the solvent.
- Ocasio-Delgado, Yessenia,De Jesús-Segarra, Jonathan,Cortés-Figueroa, José E.
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p. 3366 - 3372
(2007/10/03)
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- Transmutation of fullerenes
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Fullerenes were pyrolyzed by subliming them into a stream of flowing argon gas and then passing them through an oven heated to ～1000°C. C 76, C78, and C84 all readily lost carbons to form smaller fullerenes. In the case of C78, some isomerization was seen. Pyrolysis of 3He@C76 showed that all or most of the 3He was lost during the decomposition. C60 passes through the apparatus with no decomposition and no loss of helium.
- Cross, R. James,Saunders, Martin
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p. 3044 - 3047
(2007/10/03)
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- Kinetics of the Diels-Alder reaction between C60 and acenes
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The kinetics of the Diels-Alder reactions between C60 and the linear acenes anthracene and tetracene are studied in toluene, in the temperature range 22-63 °C. It is observed that tetracene reacts much more readily with C60 than does
- Sarova, Ginka H.,Berberan-Santos, Mário N.
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p. 402 - 407
(2007/10/03)
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- Residence time effect on fullerene yield in butadiene-based laser pyrolysis flame
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A new route for fullerene synthesis by CO2-laser pyrolysis of gas phase mixture is proposed. Small hydrocarbon molecules which absorb the laser radiation, such as butadiene, are mixed with nitrous oxide (N 2O) as oxidizer. Such a mixture allows avoiding the use of a photosensitizer as SF6 which causes contamination of the reaction zone and possibly influences the growth of fullerenic structures. This Letter also confirms the strong influence of the C/O atomic ratio in the mixture on the fullerene yield, and shows that residence time of the reactants in the pyrolysis flame and pressure influence dramatically the fullerene formation.
- Ténégal,Voicu,Armand,Herlin-Boime,Reynaud
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- Significant promotional effect of CCl4 on fullerene yield in the graphite arc-discharge reaction
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Addition of a small quantity (～3%) of CCl4 to the He atmosphere of the graphite arc-discharge reaction revealed a marked increase in fullerene yield.
- Gao, Fei,Xie, Su-Yuan,Huang, Rong-Bin,Zheng, Lan-Sun
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p. 2676 - 2677
(2007/10/03)
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- Irradiation of CW-CO2 laser on a powder target. Formation of fullerene film from graphite powder
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A process was investigated to irradiate a continuous-wave CO2 laser (4.5 kW) on graphite powder with a mean diameter of 5 μm in a flow of Ar or He gas at 30 or 200 Torr. The film produced on a Ni substrate in the Ar flow at 200 Torr showed the Raman bands of C60 and C70, and the C60/C70 ratio was estimated to be 5/1 by MALDI-TOF mass spectrometry. The film formation process is discussed on the basis of an analysis of laser-irradiated powder, which included 0.01 wt% of C60, by UV-Vis absorption, and by observations of the plumes and SEM images.
- Kano, Seisuke,Kohno, Masamichi,Sakiyama, Kaname,Sasaki, Shinya,Aya, Nobuhiro,Shimura, Hirofumi
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p. 474 - 480
(2008/10/09)
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- Functionalization of [60]fullerene and of [60]fullerene monoadducts by photochemical cycloaddition of 4-methyl-1,2,4-triazoline-3,5-dione
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The photoreactions of 4-methyl-1,2,4-triazoline-3,5-dione (NMTAD) with C60 and with several fullerene derivatives have been studied. In general, NMTAD cycloadds to C60 and to its monoadducts with closed structures in a highly regioselective [2+2] fashion at a cis-1 [6,6] double bond. Cycloadditions to azafulleroids occur by a slightly different pathway and result in partially cluster-opened bis(adducts). 1,6-Methano[60]fulleroid, however, also undergoes a [2+2+2] cycloaddition in the absence of light. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Ulmer, Lars,Siedschlag, Christina,Mattay, Jochen
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p. 3811 - 3817
(2007/10/03)
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- First soluble M @ C60 derivatives provide enhanced access to metallofullerenes and permit in vivo evaluation of Gd @ C60[C(COOH)2]10 as a MRI contrast agent
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M @ C60 and related endohedral metallofullerenes comprise a significant portion of the metallofullerene yield in the traditional arc synthesis, but their chemistry and potential applications have been largely overlooked because of their sparse solubility. In this work, procedures are described to solublize Gd @ C60 species for the first time by forming the derivative, Gd @ C60[C(COOCH2CH3)2]10, and its hydrolyzed water-soluble form, Gd @ C60[C(COOH)2]10. Imparting water solubility to Gd @ C60 permits its evaluation as a magnetic resonance imaging (MRI) contrast agent. Relaxometry measurements for Gd @ C60[C(COOH)2]10 reveal it to possess a relaxivity (4.6 mM-1 s-1 at 20 MHz and 40 °C) comparable to that of commercially available Gd(III) chelate-based MRI agents. An in vivo MRI biodistribution study in a rodent model reveals Gd @ C60[C(COOH)2]10 to possess the first non-reticuloendothelial system (RES) localizing behavior for a water-soluble endohedral metallofullerene species, consistent with its lack of intermolecular aggregation in solution as determined by light-scattering measurements. This first derivatization and use of a M @ C60 species suggests new potential for metallofullerene technologies by reducing reliance on the chromatographic purification procedures normally employed for the far less abundant M @ C82 and related endohedrals. The recognition that water-soluble fullerene derivatives can be designed to avoid high levels of RES uptake is an important step toward fullerene-based pharmaceutical development.
- Bolskar, Robert D.,Benedetto, Angelo F.,Husebo, Lars O.,Price, Roger E.,Jackson, Edward F.,Wallace, Sidney,Wilson, Lon J.,Alford, J. Michael
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p. 5471 - 5478
(2007/10/03)
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- Synthesis and characterization of mono- and bis-methano[60]fullerenyl amino acid derivatives and their reductive ring-opening retro-bingel reactions.
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The addition of N-(diphenylmethylene)glycinate esters (Ph2C=NCH2CO2R) 3-6 to [60]fullerene under Bingel conditions gives, respectively, the methano[60]fullerenyl iminoesters 7-10. Upon treatment of 7-9 with sodium cyanoborohydride, in the presence of a protic or a Lewis acid, a novel reductive ring-opening reaction occurred to give the corresponding 1,2-dihydro[60]fullerenyl glycine derivatives 11-13. Using tethered bis-N-(diphenylmethylene)glycinate esters 33 and 34derived from m- and p-benzenedimethanol scaffolds, the corresponding bis-methano[60]fullerenyl iminoesters 35-38 were synthesized under double Bingel reaction conditions. The m-benzenedimethanol derivative 33 gave the trans-4 (35) and cis-3 (36) regioisomeric bisadducts in a ratio of 80:20. The analogous para-tethered derivative 34 afforded the trans-3 (37) and trans-4 (38) regioisomers in a 80:20 ratio. The regiochemistry of the major bisadducts 35 and 37 (via the trans-esterified 39) were unequivocally determined using 2D INADEQUATE and C-C TOCSY NMR experiments. The regiochemistry of these bis-additions were unexpected on the basis of literature precedents. These results unequivocally show that the regiochemistry of tethered bis-additions is not solely dependent on the nature of the tether. A mixture of the trans-4 and cis-3 nonsymmetrical bisadducts 45 and 46 was obtained from the double-Bingel cyclopropanation of a bis-N-(diphenylmethylene)glycinate tether based on a 1,3-naphthyldimethanol scaffold. The regiochemistry of these compounds (45 and 46) was identified by correlation with the diethyl esters 40 and 47, prepared by trans-esterification of 35/45 and 36/46, respectively. The INADEQUATE and molecular modeling experiments allowed topological mapping of the fullerene surfaces of the bis-methano[60]fullerenes 38 and 42. Reductive ring-opening reactions on the tethered bis-methano[60]fullerenes 35-37, 45, and 46 gave none of the expected bis-fullerenylglycinates rather the reductive ring-opening-retro-Bingel products, the 1,2-dihydro[60]fullerenylglycinates 48, 49, 52, and 53. These compounds resulted from the reductive ring-opening of one methanoimino ester moiety and a retro-Bingel reaction of the other. Under analogous reductive ring-opening-retro-Bingel conditions, the nontethered bis-methano[60]fullerene 40 afforded the 1,2-dihydro[60]fullerenylglycinate 12. Thus, it was concluded that the tether was not the driving force for the reductive elimination of one of the methano groups.
- Burley, Glenn A,Keller, Paul A,Pyne, Stephen G,Ball, Graham E
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p. 8316 - 8330
(2007/10/03)
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- Alkylation of dihydrofullerenes
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The fulleride dianions C602- and C702- were generated by deprotonation of the corresponding hydrogenated fullerenes, 1,2-C60H2 and 1,2-C70H2. These anions were prepare
- Meier, Mark S.,Bergosh, Robert G.,Gallagher, Megan E.,Spielmann, H. Peter,Wang, Zhongwen
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p. 5946 - 5952
(2007/10/03)
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