On accuracy of the 13 C NMR chemical shift GIAO calculations of fullerene C 60 derivatives at PBE/3f approach Arthur R. Tulyabaev ⇑ , Leonard M. Khalilov Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, Ufa 450075, Russia article info Article history: Received 26 April 2011 Received in revised form 21 July 2011 Accepted 25 July 2011 Available online 4 August 2011 Keywords: NMR spectroscopy 13 C GIAO PBE/3f 2D INADEQUATE NMR C 60 Fullerene derivatives abstract The correlation analysis of the calculated by means of GIAO PBE/3f method and experimental (2D NMR INADEQUATE) 13 C NMR chemical shifts of C 60 derivatives was performed. It was shown that the compu- tational method with sufficient accuracy (r.m.s.  5 ppm) reproduces the experimental 13 C NMR chemical shifts of the sp 2 -fullerene carbon atoms uncoupled with the sp 3 -fullerene carbons. By quality description the GIAO method in PBE/3f approach best reflects the experimental 13 C NMR chemical shifts of studied in this work fullerene derivatives such as hydrofullerene C 60 H 2 , methanofullerenes, fullerene adducts of [2 + 2]- and [2 + 3]-cycloaddition, as well as azaheterofullerene. Ó 2011 Elsevier B.V. All rights reserved. 1. Introduction Since the discovery of fullerene C 60 in 1985 [1] and at a moment when it became available in bulk quantities in 1990 [2] the number of fullerene derivatives is growing. They are prospective in various fields of medicine [3], optics [4,5] and technical equipment [6]. The NMR, IR- and UV-spectroscopy, mass-spectrometry, and X-ray techniques are attributed to the identification methods of the new- ly obtained fullerene derivatives. However, the NMR spectroscopy occupies a central position among mentioned above methods, since an NMR chemical shift d is very sensitive to an electron environ- ment of magnetic nuclei [7]. In such a case the structure elucidation may be almost completely performed even there are no the crystal and enriched by 13 C isotope samples of fullerene derivatives. The literature contains only few examples demonstrating the full assignments of 13 C NMR fullerene frame resonances by means of 2D NMR INADEQUATE technique. Using the direct 13 C– 13 C coupling constants produced with this experiment, it is managed to assign all the 13 C NMR fullerene signals. So, the structure elucidation of hydrofullerenes C 60 H 2 and C 60 H 6 [8], [60]fullerenyldihydropyrrole [9], bis-methano[60]fullerenyl amino acid derivatives [10], methan- ofullerene C 61 H 2 [11], benzene adduct [12,13], N-triphenylmethyl- pyrrolidine[60]fullerene [14], osmylated tetraoxide adduct [15], 1,16-di(2-carbomethoxy-2-propyl)-1,x-dihydro[60]fullerene [16] and 1,2-methano[60]fullerene 61,61-dicarboxylate [17] was successfully carried out. However, a performing of these experi- ments is not commonly possible for the cases of the absence of en- riched samples in view of the fact that they are commercially confined. At the same time, the quantum chemistry methods are widely and successfully employed for structure elucidation, in order to determine the thermodynamically stable isomers, to reveal their reactivity and to calculate some NMR parameters such as 13 C chemical shifts of fullerene derivatives [18]. Thus, there are several works revealed the 13 C NMR chemical shift calculations by means of various quantum chemistry approaches, for instance in applica- tion to fullerene C 84 [19,20], azafullerenes (C 59 N) 2 and C 59 HN [21,22], hydroxylated fullerenes [23] and to high fullerenes [24–26]. Rather recently the quantum chemistry package PRIRODA [27] with implemented PBE/3f method [28–30] has been developed. Judicious application of computational approaches has ensured the high speed with an acceptable accuracy of calculations per- formed in the PRIRODA program. As consequence, it allowed mod- eling the structural and physicochemical properties of large organic compounds including the substituted fullerenes. So, earlier we have carried out the experimental 13 C NMR chemical shift assignments of spiro-homo- and methano[60] fullerenes by means of GIAO PBE/3f embracing the statistical analysis at the comparing experimental and calculated 13 C NMR chemical shift values [31]. In addition, as a previous experience, attributed to the structure investigations of fullerene derivatives, shows that there are no published studies concerned to the 13 C NMR chemical shift 2210-271X/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.comptc.2011.07.031 ⇑ Corresponding author. Fax: +7 347 2842750. E-mail address: tulebeich@gmail.com (A.R. Tulyabaev). Computational and Theoretical Chemistry 976 (2011) 12–18 Contents lists available at SciVerse ScienceDirect Computational and Theoretical Chemistry journal homepage: www.elsevier.com/locate/comptc