Abstract
Fullerenes are a class of three-dimensional all-carbon hollow molecules incorporating conjugated π systems. The important principle to determine the stability of fullerene cages is the isolated pentagon rule (IPR). The chemical reactivity of fullerenes is similar to that of a fairly localized, electron-deficient polyolefin. Chemical modification of fullerenes is generally classified into exohedral modification and skeletal modification. Exohedral modification affords fullerene derivatives with one or several addends covalently linked to the spherical carbon framework. The main reactions are cycloadditions, radical additions, and nucleophilic additions. Skeletal modification produces open-cage fullerenes or heterofullerenes. Open-cage fullerenes usually refer to fullerene derivatives with more than one σ-bond scission and significantly disturbed π system. Heterofullerenes are those in which one or more carbons are replaced by other non-carbon atoms such as nitrogen. The addition pattern of exohedral modification on fullerenes is generally divided into monoaddition and multiaddition. In the case of monoaddition, C60 has only two possible isomers, including 1,2- and 1,4-additions, but for C70, there are eight possible isomers, including the predominant 1,2- and 5,6-additions. As for multiaddition, low regioselectivity is generally observed and complex regioisomers are easily formed. Fullerene derivatives have displayed promising applications in many fields including material science, biological medicine, and nanotechnology due to their outstanding properties.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Similar content being viewed by others
References
Kroto HW (1987) The stability of the fullerenes Cn, with n = 24, 28, 32, 36, 50, 60 and 70. Nature 329:529–531
Kroto HW, Heath JR, O’Brien SC, Curl RF, Smalley RE (1985) C60: buckminsterfullerene. Nature 318:162–163
Krätschmer W, Lamb LD, Fostiropoulos K, Huffman DR (1990) Solid C60: a new form of carbon. Nature 347:354–358
David WIF, Ibberson RM, Matthewman JC, Prassides K, Dennis TJS, Hare JP, Kroto HW, Taylor R, Walton DRM (1991) Crystal structure and bonding of ordered carbon cluster C60. Nature 353:147–149
Ruoff RS, Tse DS, Malhotra R, Lorents DC (1993) Solubility of C60 in a variety of solvents. J Phys Chem 97:3379–3383
Semenov KN, Charykov NA, Keskinov VA, Piartman AK, Blokhin AA, Kopyrin AA (2010) Solubility of light fullerenes in organic solvents. J Chem Eng Data 55:13–36
Yurovskaya MA, Trushkov IV (2002) Cycloaddition to buckminsterfullerene C60: advancements and future prospects. Russ Chem Bull Int Ed 51:367–443
Bingel C (1993) Cyclopropanation of fullerenes. Chem Ber 126:1957–1959
Osterodt J, Vogtle F (1996) C61Br2: a new synthesis of dibromomethanofullerene and mass spectrometric evidence of the carbon allotropes C121 and C122. Chem Commun:547–548
Ohno T, Martin N, Knight B, Wudl F, Suzuki T, Yu H (1996) Quinone-type methanofullerene acceptors: precursors for organic metals. J Org Chem 61:1306–1309
Li H, Risko C, Seo JH, Campbell C, Wu G, Brédas J-L, Bazan GC (2011) Fullerene_carbene Lewis acid-base adducts. J Am Chem Soc 133:12410–12413
Banks MR, Cadogan JIG, Gosney I, Hodgson PKG, Langrige-Smith PRR, Millar JRA, Taylor AT (1995) Aziridino[2′,3′:1,2][60]fullerene. J Chem Soc Chem Commun:885–886
Heymann D, Weisman RB (2006) Fullerene oxides and ozonides. C R Chimie 9:1107–1116
Prato M, Li QC, Wudl F, Lucchini V (1993) Addition of azides to C60: synthesis of azafulleroids. J Am Chem Soc 115:1148–1150
Maggini M, Scorrano G, Prato M (1993) Addition of azomethine ylides to C60: synthesis, characterization, and functionalization of fullerene pyrrolidines. J Am Chem Soc 115:9798–9799
Shi J-L, Zhang X-F, Wang H-J, Li F-B, Zhong X-X, Liu C-X, Liu L, Liu C-Y, Qin H-M, Huang Y-S (2016) A protocol for the preparation of 2,5-diaryl fulleropyrrolidines: thermal reaction of [60]fullerene with aromatic aldehydes and arylmethanamines. J Org Chem 81:7662–7674
Tzirakis MD, Orfanopoulos M (2013) Radical reactions of fullerenes: from synthetic organic chemistry to materials science and biology. Chem Rev 113:5262–5321
Hirsch A (1995) Addition reactions of buckminsterfullerene (C60). Synthesis:895–913
Murata Y, Shiro M, Komatsu K (1997) Synthesis, X-ray structure, and properties of the first tetrakisadduct of fullerene C60 having a fulvene-type π-system on the spherical surface. J Am Chem Soc 119:8117–8118
Kampe K, Egger N, Vogel M (1993) Diamino and tetraamino derivatives of buckminsterfullerene C60. Angew Chem Intl Ed 32:1174–1176
Wang G-W, Li J-X (2006) Novel multicomponent reaction of [60]fullerene: the first example of 1,4-dipolar cycloaddition reaction in fullerene chemistry. Org Biomol Chem 4:4063–4064
Zhang W, Swager TM (2007) Functionalization of single-walled carbon nanotubes and fullerenes via a dimethyl acetylenedicarboxylate-4-dimethylaminopyridine zwitterion approach. J Am Chem Soc 129:7714–7715
Wang G-W, Komatsu K, Murata Y, Shiro M (1997) Synthesis and X-ray structure of dumb-bell-shaped C120. Nature 387:583–586
Zhang T-H, Lu P, Wang F, Wang G-W (2003) Reaction of [60]fullerene with free radicals generated from active methylene compounds by manganese(III) acetate dihydrate. Org Biomol Chem 1:4403–4407
Li F-B, Liu T-X, Wang G-W (2008) Synthesis of fullerooxazoles: novel reactions of [60]fullerene with nitriles promoted by ferric perchlorate. J Org Chem 73:6417–6420
Ma W, Wang K, Huang C, Wang H-J, Li F-B, Sun R, Liu L, Liu C-Y, Asiri AM (2020) Stereoselective synthesis of amino-substituted cyclopentafullerenes promoted by magnesium perchlorate/ferric perchlorate. Org Biomol Chem 18:964–974
Shiu L-L, Lin T-I, Peng S-M, Her G-R, Ju DD, Lin S-K, Hwang J-H, Mou CY, Luh T-Y (1994) Palladium-catalysed [3+2] cycloaddition of trimethylenemethane (TMM) and fullerene. Observation of the room-temperature fluorescence spectrum of the TMM-CGO adduct. J Chem Soc Chem Commun:647–648
Shen CKF, Chien K-M, Liu T-Y, Lin T-I, Her G-R, Luh T-Y (1995) Palladium-catalyzed [3+2] cycloaddition of 60-fullerene with cis-HOCH2CH=CHCH2OCO2Et. Tetrahedron Lett 36:5383–5384
Hashiguchi M, Watanabe K, Matsuo Y (2011) Facile fullerene modification: FeCl3-mediated quantitative conversion of C60 to polyarylated fullerenes containing pentaaryl(chloro)[60]fullerenes. Org Biomol Chem 9:6417–6421
Hashiguchi M, Obata N, Maruyama M, Yeo KS, Ueno T, Ikebe T, Takahashi I, Matsuo Y (2012) FeCl3-mediated synthesis of fullerenyl esters as low-LUMO acceptors for organic photovoltaic devices. Org Lett 14:3276–3279
Hashiguchi M, Inad H, Matsuo Y (2013) Solution-phase synthesis of dumbbell-shaped C120 by FeCl3-mediated dimerization of C60. Carbon 61:418–422
Su Y-T, Wang G-W (2013) FeCl3-mediated cyclization of [60]fullerene with N-benzhydryl sulfonamides under high-speed vibration milling conditions. Org Lett 15:3408–3411
Li Y-F, Wang K, Wang H-J, Li F-B, Sun R, Li J-X, Liu L, Liu C-Y, Asiri AM (2020) Facile access to amino-substituted cyclopentafullerenes: novel reaction of [60]fullerene with β-substituted propionaldehydes and secondary amines in the absence/presence of magnesium perchlorate. Org Biomol Chem 18:6866–6880
Liu X, Wang X-Y, Sun R, Huang M-R, Liu X-S, Wang H-J, Li F-B, Liu X-F, Liu L, Liu C-Y (2021) Fullerotetrahydroquinolines: TfOH/TsOH·H2O-mediated one-pot two-step synthesis and N-alkylation/acylation/carboamidation reaction. Adv Synth Catal 363:4399–4421
Wang H, Li F, Wang P, Sun R, Ma W, Chen M, Miao W, Liu D, Wang T (2020) Chlorinated fullerene dimers for interfacial engineering toward stable perovskite solar cells with 22.3% efficiency. Adv Energy Mater 10:2000615
Filippone S, Maroto EE, Martín-Domenech Á, Suarez M, Martín N (2009) An efficient approach to chiral fullerene derivatives by catalytic enantioselective 1,3-dipolar cycloadditions. Nat Chem 1:578–582
Marco-Martínez J, Marcos V, Reboredo S, Filippone S, Martín N (2013) Asymmetric organocatalysis in fullerenes chemistry: enantioselective phosphine-catalyzed cycloaddition of allenoates onto C60. Angew Chem Int Ed 52:5115–5119
Giovane LM, Barco JW, Yadav T, Lafleur AL, Marr JA, Howard JB, Rotello VM (1993) Kinetic stability of the fullerene C60-cyclopentadiene Diels-Alder adduct. J Phys Chem 97:8560–8561
Moonen NNP, Thilgen C, Echegoyen L, Diederich F (2000) The chemical retro-Bingel reaction: selective removal of bis(alkoxycarbonyl)methano addends from C60 and C70 with amalgamated magnesium. Chem Commun:335–336
Martín N, Altable M, Filippone S, Martín-Domenech A, Martínez-Álvarez R, Suarez M, Plonska-Brzezinska ME, Lukoyanova O, Echegoyen L (2007) Highly efficient retro-cycloaddition reaction of isoxazolino[4,5:1,2][60]- and -[70]fullerenes. J Org Chem 72:3840–3846
Wang G-W (2021) Fullerene mechanochemistry: serendipitous discovery of dumb-bell-shaped C120 and beyond. Chin J Chem 39:1797–1803
Taylor R (2001) Fluorinated fullerenes. Chem Eur J 7:4074–4083
Troyanov SI, Kemnitz E (2005) Synthesis and structures of fullerene bromides and chlorides. Eur J Org Chem:4951–4962
Troyanov SI, Kemnitz E (2012) Synthesis and structure of halogenated fullerenes. Curr Org Chem 16:1060–1078
Troshin PA, Khakina EA, Peregudov AS, Konarev DV, Soulimenkov IV, Peregudova SM, Lyubovskaya RN (2010) [C60(CN)5]-: a remarkably stable [60]fullerene anion. Eur J Org Chem:3265–3268
Wei X-W, Darwish AD, Boltalina OV, Hitchcock PB, Street JM, Taylor R (2001) The remarkable stable emerald green C60F15[CBr(CO2Et)2]3: the first [60]fullerene that is also the first [18]trannulene. Angew Chem Intl Ed 40:2989–2992
Haufler RE, Conceicao J, Chibante LPF, Chai Y, Byrne NE, Flanagan S, Haley MM, O’Brien SC, Pan C, Xiao Z, Billups WE, Ciufolini MA, Hauge RH, Margrave JL, Wilson LJ, Curl RF, Smalley RE (1990) Efficient production of C60 (buckminsterfullerene), C60H36, and the solvated buckide ion. J Phys Chem 94:8634–8636
Zhang G, Liu Y, Liang D, Gan L, Li Y (2010) Facile synthesis of isomerically pure fullerenols and formation of spherical aggregates from C60(OH)8. Angew Chem Int Ed 49:5293–5295
Matsuo Y, Nakamura E (2008) Selective multiaddition of organocopper reagents to fullerenes. Chem Rev 108:3016–3028
Gan L, Huang S, Zhang X, Zhang A, Cheng B, Cheng H, Li X, Shang G (2002) Fullerenes as a tert-butylperoxy radical trap, metal catalyzed reaction of tert-butyl hydroperoxide with fullerenes, and formation of the first fullerene mixed peroxides C60(O)(OOtBu)4 and C70(OOtBu)10. J Am Chem Soc 124:13384–13385
Schick G, Kampeb K-D, Hirsch A (1995) Reaction of [60]fullerene with morpholine and piperidine: preferred 1,4-additions and fullerene dimer formation. J Chem Soc Chem Commun:2023–2024
Isobe H, Tomita N, Nakamura E (2000) One-step multiple addition of amine to [60]fullerene. Synthesis of tetra(amino)fullerene epoxide under photochemical aerobic conditions. Org Lett 2:3663–3665
Isaacs L, Haldimann RF, Diederich F (1994) Tether-directed remote functionalization of buckminsterfullerene: regiospecific hexaadduct formation. Angew Chem Int Ed 33:2339–2342
Hummelen JC, Prato M, Wudl F (1995) There is a hole in my bucky. J Am Chem Soc 117:7003–7004
Vostrowsky O, Hirsch A (2006) Heterofullerenes. Chem Rev 106:5191–5207
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Section Editor information
Rights and permissions
Copyright information
© 2022 Springer Nature Singapore Pte Ltd.
About this entry
Cite this entry
Li, FB. (2022). Chemical Reactivity and Addition Pattern on C60 and C70. In: Lu, X., Akasaka, T., Slanina, Z. (eds) Handbook of Fullerene Science and Technology. Springer, Singapore. https://doi.org/10.1007/978-981-16-8994-9_32
Download citation
DOI: https://doi.org/10.1007/978-981-16-8994-9_32
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-16-8993-2
Online ISBN: 978-981-16-8994-9
eBook Packages: Physics and AstronomyReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics