Fullerene Genetic Code: Inheritable Stability and Regioselective C2 Assembly

A bottom-up topological pathway was established to elucidate the growth of small fullerenes and the generation of Ih-symmetric C60. In contrast to countless growth mechanisms, the model described herein has two distinctive features. First, each fullerene on the route possesses the lowest potential energy or exhibits a predominant molar fraction at elevated temperatures in the corresponding series. Second, a C2 insertion without any high-barrier rearrangement process (such as Stone–Wales transformation) can connect two adjacent molecules on the route directly. These two characteristics imply that the fullerene stability can be inherited through continuous insertion of a C2 cluster during carbon-cage enlargement. Various adducts can be generated from different active sites on the parent fullerene surface. Therefore, an investigation of the regioselectivity of C2 addition using density functional theory is reported herein for the first time. A systematic simulation demonstrates that the reaction to the most ...

[1]  S. C. O'brien,et al.  C60: Buckminsterfullerene , 1985, Nature.

[2]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[3]  A. Orden,et al.  Small carbon clusters: spectroscopy, structure, and energetics. , 1998, Chemical reviews.

[4]  Gustavo E. Scuseria,et al.  Role of sp 3 carbon and 7-membered rings in fullerene annealing and fragmentation , 1993, Nature.

[5]  H. W. Kroto,et al.  The stability of the fullerenes Cn, with n = 24, 28, 32, 36, 50, 60 and 70 , 1987, Nature.

[6]  Michael T. Bowers,et al.  Experimental evidence for the formation of fullerenes by collisional heating of carbon rings in the gas phase , 1993, Nature.

[7]  Young-Kyu Han,et al.  Structure and stability of the defect fullerene clusters of C60: C59, C58, and C57. , 2004, The Journal of chemical physics.

[8]  Stephan Irle,et al.  The C60 formation puzzle "solved": QM/MD simulations reveal the shrinking hot giant road of the dynamic fullerene self-assembly mechanism. , 2006, The journal of physical chemistry. B.

[9]  M. Dresselhaus,et al.  Topological defects in large fullerenes , 1992 .

[10]  D. Wales,et al.  Theoretical studies of icosahedral C60 and some related species , 1986 .

[11]  Xiang Zhao,et al.  Role of four-membered rings in C32 fullerene stability and mechanisms of generalized Stone-Wales transformation: a density functional theory investigation. , 2011, Physical chemistry chemical physics : PCCP.

[12]  Robert C. Haddon,et al.  .pi.-Electrons in three dimensiona , 1988 .

[13]  K. Takeuchi,et al.  Stone-Wales rearrangement pathways from the hinge-opened [2+2] C60 dimer to IPR C120 fullerenes. Vibrational analysis of intermediates , 1998 .

[14]  B. Yakobson,et al.  Real time microscopy, kinetics, and mechanism of giant fullerene evaporation. , 2007, Physical review letters.

[15]  Xiang Zhao,et al.  On the structure and relative stability of C50 fullerenes. , 2005, The journal of physical chemistry. B.

[16]  Ji-Kang Feng,et al.  Structures, stabilities, and electronic and optical properties of c(58) fullerene isomers, ions, and metallofullerenes. , 2007, Chemphyschem : a European journal of chemical physics and physical chemistry.

[17]  Roger Taylor,et al.  Isolation of Two Seven-Membered Ring C58 Fullerene Derivatives: C58F17CF3 and C58F18 , 2005, Science.

[18]  M. F. Budyka,et al.  Is C2 cluster ingested by fullerene C60 , 2002 .

[19]  Jarrold,et al.  Observation of "Stick" and "Handle" intermediates along the fullerene road , 2000, Physical review letters.

[20]  Eiji Osawa,et al.  Formalized Drawing of Fullerene Nets. 1. Algorithm and Exhaustive Generation of Isomeric Structures , 1995 .

[21]  Morinobu Endo,et al.  Formation of Carbon Nanofibers , 1992 .

[22]  A. Becke Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[23]  Tomonari Wakabayashi,et al.  A model for the C60 and C70 growth mechanism , 1992 .

[24]  Stephan Irle,et al.  Hot Giant Fullerenes Eject and Capture C2 Molecules: QM/MD Simulations with Constant Density , 2011 .

[25]  Enge Wang,et al.  Stone-Wales defects in graphene and other planar sp(2)-bonded materials , 2009 .

[26]  R. F. Curl,et al.  Probing C60 , 1988, Science.

[27]  M. Nardelli,et al.  Brittle and Ductile Behavior in Carbon Nanotubes , 1998 .

[28]  W. Krätschmer,et al.  Solid C60: a new form of carbon , 1990, Nature.

[29]  R. Smalley,et al.  Self-assembly of the fullerenes , 1992 .

[30]  Charles L. Wilkins,et al.  C62, a Non-Classical Fullerene Incorporating a Four-Membered Ring , 2000 .

[31]  Michael Sander,et al.  Synthesis of stable derivatives of c(62): the first nonclassical fullerene incorporating a four-membered ring. , 2003, Journal of the American Chemical Society.

[32]  P. C. Hariharan,et al.  The influence of polarization functions on molecular orbital hydrogenation energies , 1973 .

[33]  J. Heath Synthesis of C60from Small Carbon Clusters: A Model Based on Experiment and Theory , 1992 .

[34]  Yun Hang Hu,et al.  Ab initio quantum chemical calculations for fullerene cages with large holes , 2003 .

[35]  Gustavo E Scuseria,et al.  Scratching the surface of buckminsterfullerene: the barriers for Stone-Wales transformation through symmetric and asymmetric transition states. , 2003, Journal of the American Chemical Society.

[36]  Jun Li,et al.  Carbon arc production of heptagon-containing fullerene[68] , 2011, Nature communications.

[37]  Robert F. Curl,et al.  Photophysics of buckminsterfullerene and other carbon cluster ions , 1988 .