Structures and Electronic Properties of C₅₆Cl₈ and C₅₆Cl₁₀ Fullerene Compounds

Abstract

Stimulated by the recent observation of the first C(56)Cl(10) chlorofullerene (Science, 2004, 304, 699), we performed a systematic density functional study of the structures and properties of C(56)Cl(10) and related compounds. The fullerene derivatives C(56)Cl(8) and C(56)Cl(10) based on the parent fullerene C(56)(C(2v):011), rather than those from the most stable C(56) isomer with D(2) symmetry, are predicted to possess the lowest energies, and they are highly aromatic. Further investigations show that the heats of formation of the C(56)Cl(8) and C(56)Cl(10) fullerene derivatives are highly exothermic, that is, -48.59 and -48.89 kcal mol(-1) per Cl(2) (approaching that of C(50)Cl(10)), suggesting that adding eight (or ten) Cl atoms releases much of the strain of pure C(56)(C(2v):011) fullerene and leads to highly stable derivatives. In addition, C(56)Cl(8) and C(56)Cl(10) possess large vertical electron affinities, especially for C(56)Cl(8) with value of 3.20 eV, which is even larger than that (3.04 eV) of C(50)Cl(10), indicating that they are potential good electron acceptors with possible photonic/photovoltaic applications. Finally, the (13)C NMR chemical shifts and infrared spectra of C(56)Cl(8) and C(56)Cl(10) are simulated to facilitate future experimental identification.

Functionalization of pentagon–pentagon edges of fullerenes by cyclic polysulfides: A DFT study

“…1 [24]. Then, the C 60 (D 3 ) fullerene throughout this paper is referred to the non-IPR C 60 fullerene with D 3 symmetry and RSPI = (2,4,6,10,13,16,19,22,25,27,29,31), and C 70 (C 2v ) is referred to the non-IPR C 70 fullerene with C 2v symmetry and RSPI = (1,2,10,13,15,18,22,23,28,29,32,35). Schlegel diagrams of these structures together with their canonical spiral strips are shown in Fig.…”

“…1. We also consider C 60 fullerene with two Stone-Wales defect sites with RSPI = (2,4,13,14,16,17,19,20,22,24,26,30), C 60 (SW), leading to the formation of two pentalene-like structures on the cage of C 60 fullerene.…”

“…Moreover, many computational studies have recently been conducted to predict possible structures and electronic properties of non-IPR fullerene exoderivatives, especially for those between C 60 and C 70 or smaller fullerenes that inevitably violate the IPR according to Euler's rule [13][14][15][16]. Among the many well-known exohedral reactions developed on the nanostructures, cycloaddition reactions constitute one of the most important and versatile procedures for functionalization of fullerenes [17,18].…”

Structural stability and electronic property of C68X4 (X=H, F, and Cl) fullerene compounds

“…Paralleling the intensive achievements on synthesis and characterizations of non-IPR metallofullerenes, some hydrides and halides have also been isolated gradually. The chlorine derivatives of C 50 -C 64 have been synthesized by Xie et al [16,17] in the modified graphite arc-discharge process, and the exact structures of C 50 Cl 10 [17][18][19], C 56 Cl 10 [20,21], and C 64 Cl 4 [17,22] have been determined unambiguously with a wide range of experimental methods and density functional theory (DFT) calculations. In 2005, Troshin et al [23] have nicely synthesized milligram quantities of two stable heptagon-containing derivatives C 58 F 18 and C 58 F 17 CF 3 through fluorinating C 60 at 550 • C. More recently, a new hydride C 64 H 4 [24], with four hydrogen atoms attaching to the vertexes of a triplet of directly fused pentagons, has been successfully prepared by incorporating methane in the fullerene productions.…”

Thermochemical stabilities, electronic structures, and optical properties of C56X10 (X = H, F, and Cl) fullerene compounds

“…35 The precise structure of C 56 Cl 10 is determined unambiguously by a wide range of experimental methods and DFT calculations. 35,36 With the advances in synthesis of macroscopic quantities of C 56 Cl 10 , a theoretical understanding of the dependence of the optical and NLO properties on the molecular and electronic structures is thus of particular interest.…”