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Crystalline Functionalized Endohedral C60 Metallofullerides

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Crystalline Functionalized Endohedral C60 Metallofullerides ARTICLE DOI: 10.1038/s41467-018-05496-8 OPEN Crystalline functionalized endohedral C60 metallofullerides Ayano Nakagawa1, Makiko Nishino1, Hiroyuki Niwa1, Katsuma Ishino1, Zhiyong Wang1, Haruka Omachi 1, Ko Furukawa2, Takahisa Yamaguchi3, Tatsuhisa Kato3, Shunji Bandow4, Jeremy Rio5, Chris Ewels 5, Shinobu Aoyagi6 & Hisanori Shinohara1 Endohedral metallofullerenes have been extensively studied since the first experimental 1234567890():,; observation of La@C60 in a laser-vaporized supersonic beam in 1985. However, most of these studies have focused on metallofullerenes larger than C60 such as (metal)@C82, and there are no reported purified C60-based monomeric metallofullerenes, except for [Li@C60] + − (SbCl6) salt. Pure (metal)@C60 compounds have not been obtained because of their extremely high chemical reactivity. One route to their stabilization is through chemical functionalization. Here we report the isolation, structural determination and electromagnetic properties of functionalized crystalline C60-based metallofullerenes Gd@C60(CF3)5 and La@C60(CF3)5. Synchrotron X-ray single-crystal diffraction reveals that La and Gd atoms are indeed encapsulated in the Ih-C60 fullerene. The HOMO-LUMO gaps of Gd@C60 and La@C60 are significantly widened by an order of magnitude with addition of CF3 groups. Magnetic measurements show the presence of a weak antiferromagnetic coupling in Gd@C60(CF3)3 crystals at low temperatures. 1 Department of Chemistry and Institute for Advanced Research, Nagoya University, Nagoya 464-8602, Japan. 2 Center for Coordination of Research Facilities, Institute for Research Promotion, Niigata University, Niigata 950-2181, Japan. 3 Graduate School of Human and Environmental Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan. 4 Faculty of Science and Technology, Department of Applied Chemistry, Meijo University, Nagoya 468-8502, Japan. 5 Institut des Materiaux Jean Rouxel (IMN), Université de Nantes, CNRS UMR6502, BP32229, 44322 Nantes, France. 6 Department of Information and Basic Science, Nagoya City University, Nagoya 467-8501, Japan. Correspondence and requests for materials should be addressed to C.E. (email: [email protected]) or to H.S. (email: [email protected]) NATURE COMMUNICATIONS | (2018) 9:3073 | DOI: 10.1038/s41467-018-05496-8 | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/s41467-018-05496-8 60 fullerene is the most abundant member of the so-called isolation protocol (see Supplementary Figure 4), one may, for 1–4 – fi Cfullerene family . However, monomeric C60-based example, obtain ca. 1.0 2.0 mg of puri ed (>99.9%) endohedral metallofullerenes (i.e., fullerenes with metal Gd@C60(CF3)5 within 24 h from the initial o-xylene extraction of atom(s) encapsulated), referred to hereafter as M@C60, have not the soot containing Gd@C2m(CF3)n obtained by 10 arc-discharge been obtained in macroscopic and pure form to date. Most pre- syntheses (see Supplementary Figures 5–8). The absorption vious studies on metallofullerenes reported during the past 25 onsets of the ultraviolet-visible-near-infrared (UV-Vis-NIR) years have focused on higher fullerenes than C60 such as C80,C82, absorption spectra of CS2 solution of Gd@C60(CF3)5 and 2 and C84 , even though the presence of M@C60 has been con- La@C60(CF3)5 suggest the presence of enlarged HOMO- firmed by mass spectrometry of supersonic cluster beams in the LUMO gaps of ca. 1.2 eV approaching that of C60 (1.6 eV) (see 3 4 gas phase as well as laser-vaporized processed soot . Theoretical Supplementary Figure 9). Interestingly, Gd@C60(CF3) and calculations also suggested the stability and possible structure of Gd@C60(CF3)2 have not been solvent-extracted because of their 5–7 + − M@C60 . An exception is [Li@C60] (SbCl6) salt, which was much smaller HOMO-LUMO gaps even though mass spectro- produced by Li-ion bombardment with C60 onto a target plate in metric analysis indicates the presence of these metallofullerenes vacuum8, 9. Neutral Li+@C ∙− radicals have been obtained by in raw soot. 60 + the electrochemical reduction of cationic Li @C60; however, Because of the very high reactivity of M@C60, it has not been 10 11 Li@C60 oligomerizes and has a dimerized form in the crystal . self-evident that the metal is encapsulated in the conventional The inability to extract and purify M@C60 is due to their very truncated icosahedral Ih-C60. The C60 might have a so-called non- small highest occupied molecular orbital-lowest unoccupied isolated pentagon rule (non-IPR) structure20, 21, where two molecular orbital (HOMO-LUMO) gaps predicted, which lead to (or three) pentagons are fused with each other, since non-IPR high chemical reactivity toward surrounding soot, air, moisture, fullerenes have frequently been observed in metallofullerenes and various organic solvents. There have been, however, several during the past decade2. To answer this question, the molecular 12–15 attempts to try and extract and purify M@C60 by, for and crystal structures of Gd@C60(CF3)5 (structural isomers example, vacuum sublimation from soot followed by liquid I and II) and La@C60(CF3)5 (I) have been determined by chromatographic separation13, 14. Unfortunately, none of these synchrotron radiation single-crystal X-ray diffraction (XRD) at efforts led to the final macroscopic preparation of pure and iso- SPring-8 (see Supplementary Tables 1–5). lated M@C60. For this reason, M@C60 are often referred to as the missing metallofullerenes2, 16, 17. Synchrotron single-crystal XRD measurements. The X-ray One of the main reasons for the long-standing interest in results clearly show that the C60 cage structures of M@C60 is due to their expected novel electronic and magnetic Gd@C60(CF3)5 (I, II) and La@C60(CF3)5 (I) are very similar to fi behavior at low temperatures such as superconductivity, because that of the conventional empty C60(Ih). The ve CF3 groups of 3+ 3− the electronic band structures near the Fermi levels of M @C60 isomer I are attached to carbon atoms numbered as 6, 9, 12, 15, solids resemble those of superconducting alkali-doped C60 full- and 53 in a Schlegel diagram shown in Fig. 1a. In isomer II the 3+ 3− 18 fi erides such as (K3) C60 . If this is the case, the presence of ve CF3 groups are attached to carbon atoms numbered as 6, 9, heavy atoms like lanthanoid elements inside C60 might enhance 12, 15, and 36. In both isomers, four of the five CF3 groups are the superconducting transition temperatures19. One way to sta- attached to carbon atoms 6, 9, 12, and 15 bonded to carbon atoms bilize such species and open the HOMO-LUMO gap is through 5, 1, 2, and 3 on a pentagon. Figure 1b–e shows the molecular chemical functionalization. Here we report the macroscopic pre- structures of Gd@C60(CF3)5(I) and (II), respectively. Very inter- paration of purified (>99.9%) trifluoromethylated Gd@C60 and estingly, the remaining CF3 group is attached not to carbon atom La@C60,stableasGd@C60(CF3)3,5 and La@C60(CF3)3,5, respec- 18 but to carbon atom 53 (isomer I) or 36 (isomer II) located far tively, and their structural determination, and electronic and from the 1-2-3-4-5 pentagon. This asymmetric attachment of five fi magnetic properties. CF3 groups results in C1 symmetry. If the fth CF3 group had been attached to carbon atom 18, neighbouring carbon atom 4 on the pentagon, the molecule would have had five-fold symmetry. Results Instead of the fifth CF3 group, a Gd (La) atom inside the C60 cage Enhanced stabilization of Gd@C60 and La@C60. To stabilize is located near carbon atoms 18 and 4. The distances between the Gd@C60 and La@C60, we have employed in situ tri- Gd atom and carbon atoms 18 and 4 are ~2.38 Å in both isomers fluoromethylation during the arc-discharge synthesis of the (see Supplementary Tables 2–5). metallofullerenes developed in the present laboratory (see Sup- The selective location of the Gd (La) atom is explained in terms 11, 19 – plementary Discussion 1 and Supplementary Figure 1) . For of the elongation of C C bond lengths by the attachment of CF3 fl example, the in situ tri uoromethylation of Gd@C60 generates groups. The conventional C60(Ih) molecule consists of two kinds = – – Gd@C60(CF3)n (n 1 6) together with other sizes of tri- of C C bonds: short 6:6 bonds fusing two hexagons with a bond fl ≥ uoromethylated Gd-metallofullerenes, Gd@C2m(CF3)n (2m length of 1.39 Å and longer 6:5 bonds fusing a hexagon and a 70) (see Supplementary Figures 2 and 3 for La). The high- pentagon with a bond length of 1.45 Å. As expected, the C–C temperature arc-discharge induces evaporation of polytetra- bonds around the carbon atoms with CF3 groups attached (6, 9, fl 3 uoroethylene (PTFE) placed near the arc zone to produce CF3 12, 15, and either 53 or 36) have sp character, resulting in the radicals11. We found trifluoromethyl-derivatized metallofuller- elongation of the bonds. The 6:6 bond lengths between 6-5, 9-1, = enes, Gd@C60(CF3)n and La@C60(CF3)n (n 3, 5), were formed 12-2, and 15-3 carbon atoms are ~1.51 Å in both of the isomers fi fl ef ciently. Tri uoromethyl derivatives of Gd@C60 and La@C60 (see Supplementary Tables 2 and 5). The 6:6 bond lengths are totally soluble and stable in toluene and carbon disulfide, between 18 and 4 atoms (~1.46 Å) are also longer than the which enabled us to perform high-performance liquid chroma- normal 6:6 bond length (1.39 Å).
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