Recent progress in the studies of endohedral metallofullerenes

被引:88
作者
Liu, SY [1 ]
Sun, SQ [1 ]
机构
[1] Chinese Acad Sci, Changchun Inst Appl Chem, Changchun 130022, Peoples R China
基金
中国国家自然科学基金;
关键词
endohedral metallofullerene; synthesis; isolation; structure; property;
D O I
10.1016/S0022-328X(99)00756-1
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
This overview presents the recent progress in the area of endohedral metallofullerenes in the past several years. The important results have been summarized as follows: (1) Many metals including Group 3 metals, most of the lanthanide series elements, and Group 2 metals have been encapsulated into a fullerene cage to form mono-, di-, and trimetallofullerenes by using the arc-evaporation technique. (2) Some endohedral metallofullerenes such as Group 3 metals, most of the lanthanide series elements, Group 2 metals, and some of their isomers have been successfully isolated and purified by a two-step or several-step HPLC technique. By using high-temperature and high-pressure extraction with pyridine, Ln@C-80, Ln@C-82, and Ln2@C-80 for most rare-earth metals have been selectively extracted in high yield (about 1% of the saw soot) from fullerenes and other size metallofullerenes. (3) The endohedral nature of metallofullerenes such as Y@C-82, Sc2@C-84, and Sc@C-82 has been finally confirmed by synchrotron X-ray powder diffraction. The symmetries and the structures of metallofullerenes such as Ca@C-82(III), La-2@C-80(I-h), Sc-2@C-84(D-2d), and Sc-2@C-84(C-s) have been confirmed by NMR measurements. (Lb) The information on the electronic structures and properties of endohedral metallofullerenes has been obtained by various spectrometric means Such as EPR, W-vis-MR, XPS, CV. It is generally accepted that three-electron transfer is favorable when M = Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu but Sc, Eu, Sm, Yb, Tm, Ca, Sr, Ba prefer to donate two electrons to the fullerene cages. (5) Several chemical reactions of endohedral metallofullerenes have been reported in which reagents are disilacyclopropane, digermacyclopropane, diphenyldiazomethane, and trifluoroacetic acid. (6) Mass spectrometry provided the crucial evidence that led to the discovery of metallofullerenes in 1985 and has always played a key role in their identification and characterization, Ion-mobility measurements of gas-phase ions have obtained the information of structures and the formation mechanism of endohedral metallofullerenes. till Theoretical calculations on the endohedral metallofullerenes have made an important contribution to the studies on the symmetry of the cage, the position of metal atom(s) inside the cage, the number of electronic transfer between metal atom(s) and fullerene cage, etc. (C) 2000 Elsevier Science S.A. All rights reserved.
引用
收藏
页码:74 / 86
页数:13
相关论文
共 138 条
[1]   EXOHEDRAL DERIVATIZATION OF AN ENDOHEDRAL METALLOFULLERENE GD-AT-C-82 [J].
AKASAKA, T ;
NAGASE, S ;
KOBAYASHI, K ;
SUZUKI, T ;
KATO, T ;
YAMAMOTO, K ;
FUNASAKA, H ;
TAKAHASHI, T .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1995, (13) :1343-1344
[2]   SYNTHESIS OF THE FIRST ADDUCTS OF THE DIMETALLOFULLERENES LA-2-AT-C-80 AND SC-2-AT-C-84 BY ADDITION OF A DISILIRANE [J].
AKASAKA, T ;
NAGASE, S ;
KOBAYASHI, K ;
SUZUKI, T ;
KATO, T ;
KIKUCHI, K ;
ACHIBA, Y ;
YAMAMOTO, K ;
FUNASAKA, H ;
TAKAHASHI, T .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1995, 34 (19) :2139-2141
[3]   C-13 and La-139 NMR studies of La-2@C-80: First evidence for circular motion of metal atoms in endohedral dimetallofullerenes [J].
Akasaka, T ;
Nagase, S ;
Kobayashi, K ;
Walchli, M ;
Yamamoto, K ;
Funasaka, H ;
Kako, M ;
Hoshino, T ;
Erata, T .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1997, 36 (15) :1643-1645
[4]   EXOHEDRAL ADDUCTS OF LA-AT-C-82 [J].
AKASAKA, T ;
KATO, T ;
KOBAYASHI, K ;
NAGASE, S ;
YAMAMOTO, K ;
FUNASAKA, H ;
TAKAHASHI, T .
NATURE, 1995, 374 (6523) :600-601
[5]   Chemical derivatization of endohedral metallofullerene La@C-82 with digermirane [J].
Akasaka, T ;
Kato, T ;
Nagase, S ;
Kobayashi, K ;
Yamamoto, K ;
Funasaka, H ;
Takahashi, T .
TETRAHEDRON, 1996, 52 (14) :5015-5020
[6]   ANAEROBIC SAMPLING AND CHARACTERIZATION OF LANTHANOFULLERENES - EXTRACTION OF LAC76 AND OTHER LAC(2N) [J].
BANDOW, S ;
KITAGAWA, H ;
MITANI, T ;
INOKUCHI, H ;
SAITO, Y ;
YAMAGUCHI, H ;
HAYASHI, N ;
SATO, H ;
SHINOHARA, H .
JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (24) :9609-9612
[7]   HIGH-YIELD SYNTHESIS OF LANTHANOFULLERENES VIA LANTHANUM CARBIDE [J].
BANDOW, S ;
SHINOHARA, H ;
SAITO, Y ;
OHKOHCHI, M ;
ANDO, Y .
JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (23) :6101-6103
[8]   PREPARATION, MASS-SPECTROMETRY AND SOLID-STATE ESR SPECTROSCOPY OF ENDOHEDRAL FULLERENES [J].
BARTL, A ;
DUNSCH, L ;
KIRBACH, U .
SOLID STATE COMMUNICATIONS, 1995, 94 (10) :827-831
[9]   HETEROMETALLIC BINUCLEAR COMPLEXES INVOLVING THE MERCURY-PLATINUM BOND AS A SOURCE OF A PLATINUM CARBENOID IN REACTIONS WITH FULLERENE-60 [J].
BASHILOV, VV ;
TUMANSKII, BL ;
PETROVSKII, PV ;
SOKOLOV, VI .
RUSSIAN CHEMICAL BULLETIN, 1994, 43 (06) :1069-1072
[10]   ATOMS IN CARBON CAGES - THE STRUCTURE AND PROPERTIES OF ENDOHEDRAL FULLERENES [J].
BETHUNE, DS ;
JOHNSON, RD ;
SALEM, JR ;
DEVRIES, MS ;
YANNONI, CS .
NATURE, 1993, 366 (6451) :123-128