24 October 1997

CHEMICAL PHYSICS LETTERS

ELSEVIER
Chemical Physics Letters 278 (1997) 107- l l 0

Production and isolation of endohedral strontium- and barium-based mono-metallofullerenes: Sr/Ba@Cs2 and Sr/Ba@C84
T. John S. Dennis, Hisanori Shinohara
Department of Chemist~', Nagoya UniL,ersiO',Nagoya 464-01, Japan

Received 11 July 1997; in final form 9 August 1997

Abstract

We report the first isolation of strontium- and barium-based metallofullerenes and their characterisation by UV-vis-NIR absorption spectroscopy. The absorption spectra of the present samples (Sr/Ba@C82 and Sr/Ba@C84) show some similarity to their calcium-based analogues and are very different from those of yttrium- and lanthanum-based metallofullerenes. Assuming the barium atom to be in the 2 + state, which has an ionic radius of 1.34 A., the Ba-containing species represent the largest ionic radii-containing metallofullerenes so far isolated. 1997 Elsevier Science B.V.

1. Introduction

Endohedral metallofullerenes are a class of materials in which metal atom(s) are encaged within a fullerene network. Until recently, the metallofullerenes produced and isolated have centred on Group 3 and rare-earth elements, such as Sc, Y, La, Ce, Pr and Gd, and these are based primarily on the Cs2 fullerene [1,2]. The endohedral nature of Y@C~2 isomer I [3] and Sc2@Cs4 isomer III [4] have been confirmed by synchrotron powder X-ray diflYaction studies with the R i e t v e l d / M E M (maximum entropy method) analysis, by which such information as the nearest metal-carbon and S c - S c distances has been obtained. Furthermore, in these studies it was found that the oxidation states of the encased Y and Sc atoms were well represented by 3 + and 2 +, respectively. The divalency of the scandium atoms in 8c2@C84 is contrary to its usual trivalency but consistent with a former UPS and XPS study [5].

We have recently turned out attention to Group 2-based species with the isolation of calcium metallofullerenes [6]. One of the most important features of the calcium fullerenes is that a calcium atom can be encapsulated by a series of higher fullerenes, ranging from C72 to C100, which is to be contrasted with Group 3 metallofullerenes. Furthermore, it was found that four structural isomers of Ca@C82 [I-IV] could be produced and isolated [6] (we name these isomers of metallofullerenes as isomers I, II and so on in order of increasing retention time. There is not necessarily any correlation between, for example, isomer I of Sc@Csz and isomer I of Ca@Cs2). Here, we add to this several strontium and barium-based mono-metallofullerenes. We have found that the ultraviolet-visible-near infrared (UV-visNIR) absorption spectra of Sr@C82 and Ba@C82 have characteristic features which are consistent with the spectra of Ca@Cs2, and absent in those of La@C82, Y@C82 and Sc@C82 metallofullerenes.

0009-2614/97/$17.00 1997 Elsevier Science B.V. All rights reserved. PII S0009-26 14(97)01020-8

108

T.J.S. Dennis, H. Shinohara / Chemieal Physics Letters 278 (1997) 107 110

The results are consistently interpreted within the framework of the 2 + rather than the 3 + oxidation states of encaged Ca, Sr or Ba atom.

2. Experimental

Fullerene-soot containing Sr/Ba-based metallofullerenes was produced by the direct-current contact-arc method [1]. Graphite/metal carbide composite rods (12.5 12.5 300 mm, 0.3 atom% Sr/Ha, Toyo Tanso Co. Ltd.) were continuously arced at 250 A and 28 V, under a 12 l/rain flow of helium at 60-70 Torr. Similar to other metallofullerenes, these materials were found to be quite air a n d / o r moisture sensitive prior to extraction from the soot, and therefore, were collected under totally anaerobic conditions [1]. The fullerenes and metallofullerenes were obtained by ultrasonic extraction with carbon disulfide. Isolation was achieved by the so-called two-stage high performance liquid chromatography (HPLC) method [6,7] using two complimentary columns. Stage l a, an initial rough purification, is achieved using a Nacalai Cosmosil Buckyprep column (20 mm 250 mm) using toluene eluent at a flow rate of 18 ml/min. Further purification, stage l b, is achieved using the recycling HPLC method with the same column, eluent and flow rate. Stage 2, final purification of materials that could not be separated with the Buckyprep column, was achieved by recycling HPLC using a Regis Buckyclutcher I column (20 mm 300 mm) with toluene at a flow rate of 9.3 ml/min.

the other contained Sr/Ba@C82 (fraction la) as well as another minor isomer of C84. Recycling HPLC of fraction la, using the Buckyclutcher I column (9 cycles), gave two subfractions, which in order of elution contained Sr/Ba@Cs2 and C84. Ca@Cs2 existed in at least four isomeric forms, however, despite further recycling HPLC treatments, and careful mass spectroscopic examination of all other sub fractions of fraction 1, there was no compelling evidence for more then one isomer of Sr/Ba@C82. Buckyprep recycling of fraction 2 (3 cycles) gave four sub-bands, which in order of elution, contained: (a) a minor isomer of C84; (b) a minor isomer of Ca4; (c) Sr/Ba@C84 and C86; and (d) Cs8. After 9 cycles of fraction 2c through the Buckyclutcher, Cs6 and Sr/Ba@Cs4 were fully separated from each

C60 1

IC76
II IrCe~l
II 1111 J; ~ (h~Co~

l/i,, ,1/ B~@c,4

20

40

60

8O

<
3. Results and discussion 3.1. Isolation schemes

The isolation schemes for strontium and barium metallofullerenes are practically identical to the case of calcium metallofullerenes [6]. Sr/Ba@Cs2 was present in the shoulder following the main C84 peak (fraction 1), and Sr/Ba@Cs4 coincides with the Cs6 peak (fraction 2). Recycling HPLC of fraction 1, using the Buckyprep column (4 cycles), gave several sub-fractions. All but one of these contained minor isomers of Cs4,

40

80

120

160

R e t e n t i o n t i m e / rain
Fig. 1. (A) Stage la, (B) stage lb and (C) stage 2 in the isolation scheme for Ba@C84. The insert in part A is a 4 0 y-axis expansion of the main pattern. There is some evidence that the small peak following Ba@Cs4 is Ba@Cs0, but the quantity of the present sample is too small to be conclusive.

T.J.S. Dennis, H. Shinohara / Chemical Physics Letters 278 (1997) 107-110

109

other. Again, unlike the calcium case, there was no evidence of further separation of either Sr@C84 or Ba@C84 into isomers. As an example of the twostage HPLC process, Fig. 1 shows the HPLC separation scheme employed to obtain pure Ba@Cs4. Although the separation schemes tbr strontium and barium metallofullerenes and their calcium analogues are quite similar, there are several interesting trends with increasing atomic number of encapsulated elements. There is a trend toward slightly increasing retention time. For example, the retention times of Sr@C84 coincide with that of C86 on the Buckyprep column, whereas the retention times of 5r@C84 is a few seconds later, and that of Ca@Cs4 is about a minute less. There is also a trend of rapidly decreasing absolute yield for Group 2 monometallofullerenes analogues as the group is descended. The yields of 8r@C84 and Ba@Cs4 are about 70% and 20% of that of Ca@Cs4 (isomer I) [6], respectively. The ionic radii of Ca 2+, Sr 2+ and Ba 2+ are 0.99, 1.10 and 1.34 ,~, respectively. The larger size of the Ba 2+ could explain the lower absolute yield of Ba-metallofullerenes, as compared to Ca- and Sr-metallofullerenes. The larger sizes of Sr 2+ and Ba 2+, which may also explain the smaller number of isomers of these species, provide some insight into the mechanisms of metallofullerene formation.

.6
L~

o d~

<

Sr@C82

600

800

1000 1200 1400 1600 1800

Wavelength /nm
Fig. 2. UV-vis-NIR absorption spectra of Sr@Cs2 and Ba@Cs2.

3.2. UV-uis-NIR absorption spectroscopy

Figs. 2 and 3 show the UV-vis-NIR absorption spectra for Sr/Ba@C82 and Sr/Ba@Cs4, respectively. These allow comparisons to be made with their calcium-based, and, Group 3 and lanthanidebased analogues [ 1]. The UV-vis-NIR spectra of Sr@C84 and Ba@Cs4 are very similar to each other and to that of the more abundant isomer of Ca@Cs4 (isomer I). These results indicate that in these cases the metallofullerenes share the same respective fullerene network. Comparisons between the spectra of Sr@C82 and Ba@Cs2 are not so straightforward. However, these spectra have many characteristic features which appear at similar wavelengths, albeit with different relative intensities. They also have these features in common with the most abundant isomer of Ca@C82, suggesting that Ca@Cs2 (isomer III), Sr@Cs2 share the same fullerene isomer.

Spectroscopic similarities have also been observed between the absorption spectra of La@C82 and Y@C82 [1,2]. However, these spectra are markedly different from those obtained on Group 2-containing C82 based metallofullerenes. For example, there is a pronounced sharp feature near 1200 nm in the absorption spectra of Ca@Cs2 (III), Sr@C82 and Ba@C82. A similar feature is observed in the spectra of La@C82 and Y@Cs2, which appears near 1000 nm. Also, the 600-1000 nm region in the spectra of La@C82 and Y@C82 is quite featureless, whereas for all Ca@C82, Ba@Cs2 and Sr@C~2 this region is rich in features. The spectra of Sr and Ba metallofullerenes provide further evidence that the differences in the UV-vis-near IR absorption spectra between Group 3/lanthanide and Group 2 metallofullerenes are due to differences in electron transfer from the encaged metal atom to the fullerene cage [6]. Group 2-based metallofullerenes are expected to have an M 2+ @C~, electronic structure and diamagnetic. In contrast,

110

T.J.S. Dennis', H. Shinohara / Chemical Physics Letters 278 (1997) 107-110

~D

cage rather than the encapsulated atom. A similar result has also been obtained in a spectroscopic similarity between isomer IV of Ca 2+ @cZf and isomer I of Sc 2+ @ C ~ . This will be a useful criterion for interpreting UV-vis-near IR absorption spectra of mono-metallofullerenes. In conclusion, C82-based and Cs4-based metallofullerenes containing a single strontium/barium atom have been produced and isolated. UV-vis-NIR absorption spectra and the lack of an ESR signal suggest that these materials, together with calciumbased metallofullerenes, possess and M 2 + @ C ~ electronic structure.

<
Sr@C84

Acknowledgements
TJSD thanks the Japan Society for the Promotion of Science for the Post Doctoral Fellowship for Foreign Researchers. HS thanks the Japanese Ministry of Education, Science, Sports and Culture for Grants-in-Aid for Scientific Research on Scientific Research (A) (2) (No. 08554020) and Scientific Research (B) (2) (No. 09440198) for the financial support of the present study.

Ba@C84
I I I I I I I

600

800

1000

1200

1400

1600

1800

Wavelength / nm
Fig. 3. UV-vis-NIR absorption spectra of 8r@C84 and Ba@C84.

Group 3 metallofullerenes [8-10] are paramagnetic, existing as M 3+ @C3, - (except for Sc 2+ @C~/) [5]. The diamagnetic nature of M 2+ @C22n would also explain our failure to observe any ESR signal in either calcium metallofullerenes [6], or the present strontium and barium samples. Furthermore, the diamagnetic nature of Group 2-based metallofullerenes has been supported by a charge density measurement on Ca@C82 based on synchrotron X-ray diffraction experiments [11]. However, because of this diamagnetic behaviour of Group 2 metallofullerenes, we can determine their molecular symmetries and, correspondingly, their isomer structures by high-resolution 13C NMR measurements, as we have done on Sc 2 @Cs4 (isomer III) [7] and are also in the process of doing so on several calcium-based metallofullerenes. Differences in the UV-vis-near IR absorption spectra of Group 2-based metallofullerenes are in general dominated by effects due to the fullerene

References
[1] H. Shinohara, M. Takata, M. Sakata, T. Hashizume, T. Sakurai, Mater. Sci. Forum 232 (1996) 207. [2] R.D. Johnson, M.S. de Vries, J.R. Salem, D.S. Bethune, C.S. Yanonni, Nature 355 (1992) 239. [3] M. Takada, B. Umeda, E. Nishibori, M. Sakata, Y. Saito, M. Ohno, H. Shinohara, Nature 377 (1995) 46. [4] M. Takada, E. Nishibori, B. Umeda, M. Sakata, E. Yamamoto, H. Shinohara, Phys. Rev. Lett. 78 (1997) 3330. [5] T. Takahashi, A. Ito, M. Inakuma, H. Shinohara, Phys. Rev B 52 (1995) 13812. [6] Z. Xu, T. Nakane, H. Shinohara, J. Am. Chem. Soc. 118 (1996) 11309. [7] E. Yamamoto, M. Tansho, T. Tomiyama, H. Shinohara, Kawahara, Y. Kobayashi, J. Am. Chem. Soc. 118 (1996) 2293. [8] J.H. Weaver, Y. Chai, G.H. Kroll et al., Chem. Phys. Lett. 190 (1992) 460. [9] H. Shinohara, H. Sato, M. Ohchiochi, Y. Ando, J. Phys. Chem. 96 (1992) 3571. [10] S. Nagase, K. Kobayashi, Chem. Phys. Lett. 231 (1994) 913. [11] E. Nishibori, M. Takata, M. Sakata, T. Nakane and H. Shinohara, to be published.