Theoretical studies on structures, stabilities, NMR spectra and designing methods of dihedral fullerenes of C3 series

Abstract

Using bowl shaped carbon intermediates to construct dihedral fullerenes is an advisable method. Assuming that cap shaped C₂₁ extends the size through building pentagons and hexagons at the U and V clefts of the brims, a series of homologous carbon intermediates was generated, in which most of the members have been unknown up to now. The joins between these homologous intermediates gave the C3 dihedral series under the restriction of C ₃ symmetrical axis. The investigations point out that the stabilities of these fullerenes not only relate to the shapes of cages and the co-planarities of polygons, but also associate with the equalizations of bond lengths and the pentagonal distributions. The stabilities reveal that the pentagonal distribution in cages is not negligible to the π delocalization, besides the co-planarities of hexagons and pentagons. Analyzing the possible Stone-Wales(SW) rearrangements in those fullerenes with dehydrogenated pyracyclene units(DPUs) can help us to find out the highly stable isomers. Based on the geometrical optimizations, the calculations provided the theoretical chemical shifts of unknown fullerenes and the data reconfirmed the existence of members C₇₈ and C₈₄. The symmetry adaptation analyses for the frontier orbitals support the formative mechanism of consecutive pentagonal and hexagonal fusions, but the simulated routes are more complicated than the pentagon road(PR) mechanism, which include not only C₂ but also C₃ additive reactions.

Keywords

Dihedral fullerene / Curvature / Distortion / Pentagon and hexagon / Chemical shift / Stone-Wales(SW) arrangement / Density functional theory

References

[1] Kroto H W, Heath J R, O’Brien S C, Curl R F, Smalley R E. Nature, 1985, 318: 162.

[2] Krätschmer W, Lamb L D, Fostiropoulos K, Huffman D R. Nature, 1990, 347: 354.

[3] Li P. Science China Chemistry B, 2012, 55: 1856.

[4] Smalley R E. Acc. Chem. Res., 1992, 25: 98.

[5] Chen Z F, Thiel W. Chem. Phys. Lett., 2003, 367: 15.

[6] Shao N, Gao Y, Zeng X C. J. Phys. Chem. C, 2007, 111: 17671.

[7] Cai W, Shao L N, Shao X G, Guo Q X. J. Chem. Phys., 2005, 122: 184318-1.

[8] Diederich F, Whetten R L, Thilgen C, Ettl R, Chao I, Alvarez M M. Science, 1991, 254: 1768.

[9] Kikuchi K, Nakahara N, Wakabayashi T, Suzuki S, Shiromaru H, Miyake Y, Saito K, Ikemoto I, Kainosho M, Achiba Y. Nature, 1992, 357: 142.

[10] Taylor R, Langley G J, Dennis T S, Kroto H W, Walton D R M. J. Chem. Soc., Chem. Commun., 1992, 1043.

[11] Taylor R, Langley G J, Avent A G, Dennis T J S, Kroto H W, Walton D R M. J. Chem. Soc. Perkin Trans. 2, 1993, 1029.

[12] Avent A G, Dubois D, Pénicaud A, Taylor R. J. Chem. Soc., Perkin Trans. 2, 1997, 1907.

[13] Tagmatarchis N, Avent A G, Prassides K, Taylor R. Chem. Commun, 1999, 1023.

[14] Harris P J F. Carbon Nanotube Science: Synthesis, Properties, and Applications, 2010, Cambridge: Cambridge University Press 20.

[15] Sun G, Kertesz M. J. Phys. Chem. A, 2000, 104: 7398.

[16] Sun G, Kertesz M. J. Phys. Chem. A, 2001, 105: 5212.

[17] Becke A D. J. Chem. Phys., 1993, 98: 5648.

[18] Vosko S H, Wilk L, Nusair M. Can. J. Phys., 1980, 58: 1200.

[19] Lee C, Yang W, Parr R G. Phys. Rev. B, 1988, B37: 785.

[20] Miehlich B, Savin A, Stoll H, Preuss H. Chem. Phys. Lett., 1989, 157: 200.

[21] Botao F, Ruisheng Z, Jianhua Y. Computer Chemistry and Molecular Design, 2009, Beijing: Higher Education Press.

[22] Trindle C, Shillady D. Electronic Structure Modeling: Connections Between Theory and Software, 2008, New York: CRC Press.

[23] Piela L. Ideas of Quantum Chemistry, 2007, Amsterdam: Elsevier 658.

[24] Glendening E D, Reed A E, Carpenter J E, Weinhold F. NBO Version 3.1 in Gaussian 03 D01, 2005, Wallingford CT: Gaussian Inc.

[25] Foster J P, Weinhold F. J. Am. Chem. Soc., 1980, 102: 7211.

[26] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Montgomery J A, Vreven J T, Kudin K N, Burant J C, Millam J M, Iyengar S S, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson G A, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox J E, Hratchian H P, Cross J B, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann R E, Yazyev O, Austin A J, Cammi R, Pomelli C, Ochterski J W, Ayala P Y, Morokuma K, Voth G A, Salvador P, Dannenberg J J, Zakrzewski V G, Dapprich S, Daniels A D, Strain M C, Farkas O, Malick D K, Rabuck A D, Raghavachari K, Foresman J B, Ortiz J V, Cui Q, Baboul A G, Clifford S, Cioslowski J, Stefanov B B, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin R L, Fox D J, Keith T, Al-Laham M A, Peng C Y, Nanayakkara A, Challacombe M, Gill P M W, Johnson B, Chen W, Wong M W, Gonzalez C, Pople J A. Gaussian 03 D01, 2005, Wallingford CT: Gaussian Inc.

[27] Saunders M, Jimenez-Vazquez H A, Cross R J, Billups W E, Gesenberg C, Gonzalez A, Luo W, Haddon R C, Diederich F, Herrmann A. J. Am. Chem. Soc., 1995, 117: 9305.

[28] Kareev I E, Popov A A, Kuvychko I V, Shustova N B, Lebedkin S F, Bubnov V P, Anderson O P, Seppelt K, Strauss S H, Boltalina O V. J. Am. Chem. Soc., 2008, 130: 13471.

[29] Shustova N B, Kuvychko I V, Bolskar R D, Seppelt K, Strauss S H, Popov A A, Boltalina O V. J. Am. Chem. Soc., 2006, 128: 15793.

[30] Johnston R L. Atomic and Molecular Clusters, 2002, London: Taylor and Francis Press 158.

[31] Reed A E, Weinstock R B, Weinhold F. J. Chem. Phys., 1985, 83: 735.

[32] Ebbesen T W, Tabuchi J, Tanigaki K. Chem. Phys. Lett., 1992, 191: 336.

[33] Bate K R, Scuseria G E. J. Phys. Chem. A, 1997, 101: 3038.

[34] Fukui K. Science, 1982, 4574: 747.

[35] Li P. J. At. Mol. Sci., 2012, 3: 308.

[36] Yang S, Taylor K J, Craycraft M J, Conceicao J, Pettiette C L, Cheshnovsky O, Smalley R E. Chem. Phys. Lett., 1988, 144: 431.