Research ArticlesNo Access

ELECTRON TRANSFER MAKES D_3h (78:5) CAGE EASY TO FORM M₂@C₇₈(M = La, Ce): A RELATIVISTIC DENSITY-FUNCTIONAL THEORY STUDY

CE HAO

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, P. R. China

Corresponding author.

Search for more papers by this author

HONGJIANG LI

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, P. R. China

Search for more papers by this author

GUORONG JIA

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, P. R. China

Search for more papers by this author

SHENMIN LI

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, P. R. China

Liaoning Province Key Laboratory of Bio-Organic Chemistry, Dalian University, Dalian, 116622, P. R. China

Search for more papers by this author

, and

JIESHAN QIU

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, P. R. China

Corresponding author.

Search for more papers by this author

https://doi.org/10.1142/S0219633612500137Cited by:1 (Source: Crossref)

Abstract

Applying relativistic density functional theory to isomers of C₇₈ and M₂@C₇₈(M = La, Ce), we calculate and analyze the relative energies and HOMO–LUMO gaps of neutral and hexaanion ( -6 charged) C₇₈ isomers. Our results indicate that the (5) isomer is the most stable, and it illustrate that electron transfer plays an important role in controlling the stability of endohedral metallofullerenes. We also calculate the electronic structures of there neutral isomers, and based on their LUMO + 2 and LUMO + 3 gaps, we explain why it is easier to encage two metal atoms in D_3h′ (78:5). To further elucidate this issue, we theoretically characterize M₂@C₇₈(M = La, Ce) and compare the relative energies and the HOMO–LUMO gap of the two isomers M₂@C₇₈ (4) and the M₂@C₇₈ (5) (M = La, Ce). The results indicate that M₂@C₇₈ (5) is more stable than M₂@C₇₈ (4). Furthermore, the good agreement between the experimental and computed ¹³C NMR chemical shift of the isomer M₂@C₇₈ (5) provided strong evidence that M₂@C₇₈ forms a D_3h′ (78:5) cage.

Keywords:

References

Y. Chaiet al., J. Phys. Chem. 95, 7564 (1991), DOI: 10.1021/j100173a002. Crossref, Web of Science, Google Scholar
H. W. Kroto, Nature 329, 529 (1987), DOI: 10.1038/329529a0. Crossref, Web of Science, Google Scholar
P. W. Fowler, J. Phys. Chem. Solid. 54, 1825 (1993), DOI: 10.1016/0022-3697(93)90295-3. Crossref, Web of Science, Google Scholar
M.-F. Fan, Z. Lin and S. Yang, J. Mol. Struct. (THEOCHEM) 337, 231 (1995), DOI: 10.1016/0166-1280(95)04137-U. Crossref, Web of Science, Google Scholar
P. W. Fowler and F. Zerbetto, Chem. Phys. Lett. 243, 36 (1995), DOI: 10.1016/0009-2614(95)00849-Y. Crossref, Web of Science, Google Scholar
T. Akasakaet al., Angew. Chem, Int. Ed. Engl. 36, 1643 (1997), DOI: 10.1002/anie.199716431. Crossref, Web of Science, Google Scholar
H. Katoet al., J. Am. Chem. Soc. 125, 7782 (2003), DOI: 10.1021/ja0353255. Crossref, Web of Science, Google Scholar
C. R. Wanget al., Nature 408, 426 (2001), DOI: 10.1038/35044195. Crossref, Web of Science, Google Scholar
M. Takataet al., Chem. Phys. Lett. 372, 512 (2003), DOI: 10.1016/S0009-2614(03)00423-8. Crossref, Web of Science, Google Scholar
Z. Q. Shiet al., Angew. Chem, Int. Ed. 45, 2107 (2006), DOI: 10.1002/anie.200503705. Crossref, Web of Science, Google Scholar
P. Jinet al., Phys. Chem. Chem. Phys. 12, 12442 (2010), DOI: 10.1039/b923106d. Crossref, Web of Science, Google Scholar
A. A. Popovet al., J. Phys. Chem. B. 111, 3363 (2007), DOI: 10.1021/jp068661r. Crossref, Web of Science, Google Scholar
X. Wuet al., J. Nanosci Nanotech 7, 1346 (2007), DOI: 10.1166/jnn.2007.313. Crossref, Web of Science, Google Scholar
T. Yumuraet al., J. Phys. Chem. B. 109, 20251 (2005), DOI: 10.1021/jp0519767. Crossref, Web of Science, Google Scholar
P. W. Fowler and D. E. Manoloupoulus, An Atlas of Fullerenes (Oxford University Press, Oxford, United Kingdom, 1995) p. 254. Google Scholar
F. Diederichet al., Science 254, 1768 (1991). Crossref, Web of Science, Google Scholar
K. Kikuchiet al., Nature 357, 142 (1992), DOI: 10.1038/357142a0. Crossref, Web of Science, Google Scholar
R. Tayloret al., J. Chem. Soc, Chem. Commun. 1043 (1992), DOI: 10.1039/c39920001043. Google Scholar
G. Sun and M. Kertesz, J. Phys. Chem. A. 104, 7398 (2000), DOI: 10.1021/jp001272r. Crossref, Web of Science, Google Scholar
T. S. Chu, Y. Zhang and K. L. Han, Int. Rev. Phys. Chem. 25, 201 (2006), DOI: 10.1080/01442350600677929. Crossref, Web of Science, Google Scholar
K.-L. Han and G.-Z. He, J. Photochem. Photobiol. C: Photochem. Rev. 8, 55 (2007). Crossref, Web of Science, Google Scholar
T. S. Chu and K. L. Han, Phys. Chem. Chem. Phys. 10, 2431 (2008), DOI: 10.1039/b715180b. Crossref, Web of Science, Google Scholar
F. Yuet al., J. Am. Chem. Soc. 133, 11030 (2011), DOI: 10.1021/ja202582x. Crossref, Web of Science, Google Scholar
G. J. Zhao and K. L. Han, Acc. Chem. Res. 25, 119 (1992). Web of Science, Google Scholar
R. Tayloret al., J. Chem. Soc, Perkin. Trans. 2, 1029 (1993). Google Scholar
S. I. Troyanov and E. Kemnitz, Eur. J. Org. Chem. 3916 (2003), DOI: 10.1002/ejoc.200300358. Google Scholar
Z. Slaninaet al., J. Mol. Struct. (Theochem) 279, 213 (1993). Crossref, Google Scholar
B. L. Zhang, C. Z. Wang and K. M. Ho, Chem. Phys. Lett. 193, 225 (1992), DOI: 10.1016/0009-2614(92)85659-X. Crossref, Web of Science, Google Scholar
E. Osawaet al., J. Chem. Soc, Perkin. Trans. 2, 943 (1998). Google Scholar
M. Bühl and C. van Wüllen, Chem. Phys. Lett. 247, 63 (1995). Crossref, Web of Science, Google Scholar
G. Sun and M. Kertesz, J. Phys. Chem. A. 104, 7398 (2000), DOI: 10.1021/jp001272r. Crossref, Web of Science, Google Scholar
T. Heineet al., J. Phys. Chem. 103, 8738 (1999). Crossref, Web of Science, Google Scholar
N. B. Shustovaet al., J. Am. Chem. Soc. 128, 15793 (2006), DOI: 10.1021/ja065178l. Crossref, Web of Science, Google Scholar
Shustova NB, Newell BS, Miller SM, Anderson OP, Bolskar RD, Seppelt K, Popov AA, Boltalina OV, Strauss SH, Angew Chem 119:4189, 2007; Angew Chem, Int Ed 46:4111, 2007 . Google Scholar
K. Simeonovet al., Angew. Chem, Int. Ed. 47, 6283 (2008), DOI: 10.1002/anie.200801922. Crossref, Web of Science, Google Scholar
P. B. Caoet al., J. Am. Chem. Soc. 126, 9164 (2004), DOI: 10.1021/ja048599g. Crossref, Web of Science, Google Scholar
B. P. Caoet al., J. Am. Chem. Soc. 130, 983 (2008), DOI: 10.1021/ja076462v. Crossref, Web of Science, Google Scholar
M. Yamadaet al., Chem. Commun 558 (2008), DOI: 10.1039/b712568b. Google Scholar
A. A. Popovet al., J. Phys. Chem. B. 111, 3363 (2007), DOI: 10.1021/jp068661r. Crossref, Web of Science, Google Scholar
J. Zhanget al., J. Phys. Chem. C. 111, 7862 (2007), DOI: 10.1021/jp0686590. Crossref, Web of Science, Google Scholar
A. G. Aventet al., J. Chem. Soc, Perkin. Trans. 2, 1907 (1997). Google Scholar
G.-J. Zhao and K.-L. Han, J. Phys. Chem. A. 111, 2469 (2007), DOI: 10.1021/jp068420j. Crossref, Web of Science, Google Scholar
G.-J. Zhao and K.-L. Han, Biophys. J. 94, 38 (2008), DOI: 10.1529/biophysj.107.113738. Crossref, Web of Science, Google Scholar
G.-J. Zhaoet al., J. Phys. Chem. B. 111, 8940 (2007), DOI: 10.1021/jp0734530. Crossref, Web of Science, Google Scholar
G.-J. Zhao, K.-L. Han and P. J. Stang, J. Chem. Theory. Computat. 5, 1955 (2009), DOI: 10.1021/ct900216m. Crossref, Web of Science, Google Scholar
G.-J. Zhaoet al., J. Phys. Chem. A. 114, 9007 (2010), DOI: 10.1021/jp105009t. Crossref, Web of Science, Google Scholar
G. J. Zhaoet al., J. Phys. Chem. A. 115, 6390 (2011), DOI: 10.1021/jp202825q. Crossref, Web of Science, Google Scholar
K. Kobayashi and S. Nagase , Endofullerenes: A New Family of Carbon Clusters , eds. T. Akasaka and S. Nagase ( Kluwer Academic , Netherlands , 2001 ) . Google Scholar
S. Stevensonet al., Nature 408, 427 (2000). Crossref, Web of Science, Google Scholar
J. M. Campanera, C. Bo and J. M. Poblet, Angew. Chem, Int. Ed. 44, 7230 (2005), DOI: 10.1002/anie.200501791. Crossref, Web of Science, Google Scholar
A. A. Popov and L. Dunsch, J. Am. Chem. Soc. 129, 11835 (2007), DOI: 10.1021/ja073809l. Crossref, Web of Science, Google Scholar
C. M. Beaverset al., J. Am. Chem. Soc. 131, 11519 (2009), DOI: 10.1021/ja903741r. Crossref, Web of Science, Google Scholar
J.-I. Aihara, J. Phys. Chem. A. 106, 11371 (2005), DOI: 10.1021/jp021390+. Crossref, Web of Science, Google Scholar
X. Xuet al., Chem. Eur. J. 12, 562 (2006), DOI: 10.1002/chem.200500210. Crossref, Web of Science, Google Scholar
T. Suzukiet al., Angew. Chem, Int. Ed. 34, 1094 (1995). Crossref, Web of Science, Google Scholar
N. Luet al., J. Phys. Chem. C. 115, 11991 (2011), DOI: 10.1021/jp204476q. Crossref, Web of Science, Google Scholar
J. Zhouet al., J. Phys. Chem. C. 115, 253 (2011), DOI: 10.1021/jp105121y. Crossref, Web of Science, Google Scholar
L. S. Xuet al., J. Phys. Chem. C. 115, 6815 (2011), DOI: 10.1021/jp200423j. Crossref, Web of Science, Google Scholar