PMID- 31241888
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20190923
IS  - 1520-4898 (Electronic)
IS  - 0001-4842 (Linking)
VI  - 52
IP  - 7
DP  - 2019 Jul 16
TI  - Trapping Metallic Oxide Clusters inside Fullerene Cages.
PG  - 1802-1811
LID - 10.1021/acs.accounts.9b00206 [doi]
AB  - The sub-nanometer sized void inside a fullerene cage permits the accommodation of 
      a single atom, atomic cluster, or even small molecule, resulting in the formation 
      of endohedral fullerenes. Particularly, clusterfullerenes can be formed by 
      encapsulating multiple metallic ions in most cases along with nonmetal ions 
      (i.e., N(3-), C(2)(2-), S(2-), O(2-)) inside the fullerene cage. Such an 
      association makes clusterfullerene more functional than empty fullerenes and 
      conventional mono-metallofullerenes. To date, a variety of clusterfullerenes have 
      been reported, including metal nitrides, carbides, oxides, sulfides, cyanides, 
      and so on. Among them, oxide clusterfullerenes (OCFs) can contain variable oxide 
      clusters (i.e., M(4)O(2), M(4)O(3), M(3)O, and M(2)O; M = Sc or other metal), 
      yielding one of the most versatile families. Thus, OCFs may provide a more 
      convenient platform for developing new functional molecules and for studying 
      previously less-explored topics such as formation mechanisms of 
      clusterfullerenes. In this Account, we review recent progress in the field of 
      OCFs, including their synthesis, isolation, and structural and electrochemical 
      studies as well as the preliminary exploration into their potential functions and 
      applications. Thanks to the concrete crystallographic results of an OCF series, 
      we can track the transition of endohedral cluster and fullerene cage. It is 
      suggested that the configuration and internal dynamics of the oxide cluster are 
      highly dependent on not only the cage size but also cage structure. On the other 
      hand, based on the experimental observations, two competitive transformation 
      pathways are established for the majority of OCFs, verifying the bottom-up or 
      top-down formation mechanism. It is also found that the redox behaviors of OCFs 
      are more or less comparable to their isoelectronic species with common cage 
      structure and similar cluster geometry but varied greatly with the cluster 
      variety (i.e., Sc(2)O vs Sc(4)O(2-3)). The mechanism behind such phenomena has 
      been discussed. In addition, the potential of Dy-based OCFs as single molecular 
      magnets (SMMs) is presented theoretically. Nevertheless, experimental advance 
      remains to be achieved.
FAU - Feng, Lai
AU  - Feng L
AUID- ORCID: 0000-0003-0278-5502
AD  - College of Energy, Soochow Institute for Energy and Materials Innovations & Key 
      Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of 
      Jiangsu Province , Soochow University , Suzhou 215006 , China.
FAU - Hao, Yajuan
AU  - Hao Y
AD  - College of Energy, Soochow Institute for Energy and Materials Innovations & Key 
      Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of 
      Jiangsu Province , Soochow University , Suzhou 215006 , China.
FAU - Liu, Along
AU  - Liu A
AD  - College of Energy, Soochow Institute for Energy and Materials Innovations & Key 
      Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of 
      Jiangsu Province , Soochow University , Suzhou 215006 , China.
FAU - Slanina, Zdenek
AU  - Slanina Z
AD  - Department of Chemistry and Biochemistry , University of Arizona , Tucson , 
      Arizona 85721-0041 , United States.
LA  - eng
PT  - Journal Article
DEP - 20190626
PL  - United States
TA  - Acc Chem Res
JT  - Accounts of chemical research
JID - 0157313
SB  - IM
EDAT- 2019/06/27 06:00
MHDA- 2019/06/27 06:01
CRDT- 2019/06/27 06:00
PHST- 2019/06/27 06:00 [pubmed]
PHST- 2019/06/27 06:01 [medline]
PHST- 2019/06/27 06:00 [entrez]
AID - 10.1021/acs.accounts.9b00206 [doi]
PST - ppublish
SO  - Acc Chem Res. 2019 Jul 16;52(7):1802-1811. doi: 10.1021/acs.accounts.9b00206. 
      Epub 2019 Jun 26.