99685-96-8Relevant articles and documents
Cage-Expansion of Fullerenes
Zhang, Sheng,Hashikawa, Yoshifumi,Murata, Yasujiro
supporting information, p. 12450 - 12454 (2021/08/20)
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.
Stereoselective synthesis of amino-substituted cyclopentafullerenes promoted by magnesium perchlorate/ferric perchlorate
Ma, Wan,Wang, Kun,Huang, Cheng,Wang, Hui-Juan,Li, Fa-Bao,Sun, Rui,Liu, Li,Liu, Chao-Yang,Asiri, Abdullah M.
supporting information, p. 964 - 974 (2020/02/15)
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.
Lewis base-catalyzed double nucleophilic substitution reaction of N-tosylaziridinofullerene with thioureas or guanidines
Meng, Qi,Cheng, Jun-Yu,Miao, Chun-Bao,Sun, Xiao-Qiang,Yang, Hai-Tao
, p. 2566 - 2570 (2017/06/13)
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
DMAP-Mediated Synthesis of Fulleropyrrolines: Reaction of [60]Fullerene with Aromatic Aldehydes and Arylmethanamines in the Absence or Presence of Manganese(III) Acetate
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.
, p. 9751 - 9764 (2017/09/22)
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.
Lu2@C2n (2n = 82, 84, 86): Crystallographic Evidence of Direct Lu-Lu Bonding between Two Divalent Lutetium Ions Inside Fullerene Cages
Shen, Wangqiang,Bao, Lipiao,Wu, Yongbo,Pan, Changwang,Zhao, Shasha,Fang, Hongyun,Xie, Yunpeng,Jin, Peng,Peng, Ping,Li, Fang-Fang,Lu, Xing
supporting information, p. 9979 - 9984 (2017/08/02)
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.
CF2-Bridged C60 Fullerene Dimers and their Optical Transitions
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
, p. 3540 - 3543 (2017/11/22)
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.
Cu-catalyzed C-H amination of Hydrofullerenes leading to 1,4-Difunctionalized Fullerenes
Si, Weili,Lu, Shirong,Bao, Ming,Asao, Naoki,Yamamoto, Yoshinori,Jin, Tienan
supporting information, p. 620 - 623 (2014/04/03)
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.
Method for the synthesis of amine-functionalized fullerenes involving set-promoted photoaddition reactions of -silylamines
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.
supporting information, p. 6946 - 6958 (2014/08/18)
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.
Modification of fulleropyrazolines modulates their cleavage by light
Rutte, Reida N.,Parsons, Thomas B.,Davis, Benjamin G.
supporting information, p. 12297 - 12299 (2015/02/19)
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
Facile catch and release of fullerenes using a photoresponsive molecular tube
Kishi, Norifumi,Akita, Munetaka,Kamiya, Motoshi,Hayashi, Shigehiko,Hsu, Hsiu-Fu,Yoshizawa, Michito
, p. 12976 - 12979 (2013/09/24)
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.
