This article reviews recent developments and applications in the area of computational electrochemistry. Our focus is on predicting the reduction potentials of electron transfer and other electrochemical reactions and half-reactions in both aqueous and nonaqueous solutions. Topics covered include various computational protocols that combine quantum mechanical electronic structure methods (such as density functional theory) with implicit-solvent models, explicit-solvent protocols that employ Monte Carlo or molecular dynamics simulations (for example, Car–Parrinello molecular dynamics using the grand canonical ensemble formalism), and the Marcus theory of electronic charge transfer. We also review computational approaches based on empirical relationships between molecular and electronic structure and electron transfer reactivity. The scope of the implicit-solvent protocols is emphasized, and the present status of the theory and future directions are outlined.

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Computational electrochemistry: prediction of liquid-phase reduction potentials

Endohedral metallofullerenes (EMFs), a new class of hybrid molecules formed by encapsulation of metallic species inside fullerene cages, exhibit unique properties that differ distinctly from those of empty fullerenes because of the presence of metals and their hybridization effects via electron transfer. This critical review provides a balanced but not an exhaustive summary regarding almost all aspects of EMFs, including the history, the classification, current progress in the synthesis, extraction, isolation, and characterization of EMFs, as well as their physiochemical properties and applications in fields such as electronics, photovoltaics, biomedicine, and materials science. Emphasis is assigned to experimentally obtained results, especially the X-ray crystallographic characterizations of EMFs and their derivatives, rather than theoretical calculations, although the latter has indeed enhanced our knowledge of metal–cage interactions. Finally, perspectives related to future developments and challenges in the research of EMFs are proposed. (381 references)

Current status and future developments of endohedral metallofullerenes

In this tutorial review taking X-ray crystallographically characterized compounds as a starting point a walk is taken through the electronic and structural properties of endohedral metallofullerenes After classification of the fullerenes according to the encapsulated guest, particular attention is given to identifying factors that determine the selection of a particular carbon cage network by the internal metal cluster Some of the physical rules that determine which particular fullerene cage is formed will be discussed Concepts such as charge transfer between the cage and the guest metal ions, the topology of the cage, the separations between the 12 pentagons on the fullerene surface, and the effect of entropic factors are used to rationalize the selection of a particular cage The roles of electrochemistry and vibrational spectroscopy in combination with theoretical calculations are considered in understanding the structures of the endohedral fullerenes

Endohedral metallofullerenes: a unique host–guest association

Fullerenes have the characteristic of a hollow interior, and this unique feature triggers intuitive inspiration to entrap atoms, ions or clusters inside the carbon cage in the form of endohedral fullerenes. In particular, upon entrapping an otherwise unstable metal cluster into a carbon cage, the so-called endohedral clusterfullerenes fulfil the mutual stabilization of the inner metal cluster and the outer fullerene cage with a specific isomeric structure which is often unstable as an empty fullerene. A variety of metal clusters have been reported to form endohedral clusterfullerenes, including metal nitrides, carbides, oxides, sulfides, cyanides and so on, making endohedral clusterfullerenes the most variable and intriguing branch of endohedral fullerenes. In this review article, we present an exhaustive review on all types of endohedral clusterfullerenes reported to date, including their discoveries, syntheses, separations, molecular structures and properties as well as their potential applications in versatile fields such as biomedicine, energy conversion, and so on. At the end, we present an outlook on the prospect of endohedral clusterfullerenes.

When metal clusters meet carbon cages: endohedral clusterfullerenes

Unambiguous X-ray crystallographic results of the carbene adduct of Sc2C82 reveal a new carbide cluster metallofullerene with the unexpected C2v(5)-C80 cage, that is, Sc2C2@C2v(5)-C80. More interestingly, DFT calculations and NMR results disclose that the dynamic motion of the internal Sc2C2 cluster depends strongly on temperature. At 293 K, the cluster is fixed inside the cage with two nonequivalent Sc atoms on the mirror plane, thereby leading to Cs symmetry of the whole molecule. However, when the temperature increases to 413 K, the 13C and 45Sc NMR spectra show that the cluster rotates rapidly inside the C2v(5)-C80 cage, featuring two equivalent Sc atoms and weaker metal−cage interactions.

Sc2C2@C80 Rather than Sc2@C82: Templated Formation of Unexpected C2v(5)-C80 and Temperature-Dependent Dynamic Motion of Internal Sc2C2 Cluster

A series of13C-enriched monoytterbium endohedral metallofullerenes (EMFs)—Yb@C2n (n = 40, 41, 42)—was synthesized and isolated. Their cage structures were systematically determined for the first time using computational and experimental 13C NMR studies. The results revealed that all isomers adopt cage structures conforming to the isolated pentagon rule. In detail, Yb@C80 possesses the C2v(3) cage; Yb@C82(I, II, III) bear Cs(6), C2(5), and C2v(9) cages, respectively; and Yb@C84(II, III, IV) have C2(13), C1(12), and C2(11) cage structures, respectively. This is the first report describing C2(13)-C84 and C1(12)-C84 cage structures. It is noteworthy that the cage structures found for mono-EMFs generally differ from either the corresponding empty fullerenes or the related EMFs encapsulating more than one metal atom, indicating that the metal atom inside the fullerene cage plays an important role in determining the EMF structure. On the basis of the fact that the structure of Yb@C2(13)-C84 resembles that of Yb@...

Yb@C2n (n = 40, 41, 42): New Fullerene Allotropes with Unexplored Electrochemical Properties

The thermal reaction of the endohedral metal- lofullerene La2@D2(10611)-C72, which contains two pentalene units at opposite ends of the cage, with 5,6-diphenyl-3-(2- pyridyl)-1,2,4-triazine proceeded selectively to afford only two bisfulleroid isomers. The molecular structure of one isomer was determined using single-crystal X-ray crystallography. The results suggest that the (4+2) cycloaddition was initiated in a highly regioselective manner at the CC bond connecting two pentagon rings of C72. Subsequent intramolecular electrocyc- lization followed by cycloreversion resulted in the formation of an open-cage derivative having three seven-membered ring orifices on the cage and a significantly elongated cage geometry. The reduction potentials of the open-cage derivatives were similar to those of La2@D2-C72 whereas the oxidation potentials were shifted more negative than those of La2@D2- C72. These results point out that further oxidation could occur

Regioselective Cage Opening of La 2 @D 2 (10611)-C 72 with 5,6-Diphenyl- 3-(2-pyridyl)-1,2,4-triazine**

Yb@C2n (n = 40, 41, 42): New Fullerene Allotropes with Unexplored Electrochemical Properties.

There have been many examples of synthesizing multinuclear lanthanide clusters of special shapes, such as spherical, cage-shaped, tubular, and so on. However, synthesizing multinuclear lanthanide clusters with distinct layered structures possess a challenge. We use the ligands 2,3-dihydroxybenzaldehyde, benzohydrazide and pyridin-2-ylmethanamine to obtain a single layer of six-core lanthanide clusters [Dy6(μ3-O)(μ3-OH)4(L2)3(L3)3(L4)3(H2O)3]Cl6·CH3OH (1) and [Gd6(μ3-O)(μ3-OH)4(L2)3(L3)3(L4)3(H2O)2(CH3OH)]Cl6·CH3OH·3CH3CN (2). The central metal ion of cluster 1 presents a triangular lattice shape. We changed the ligands to 2-hydroxy-3-methoxybenzaldehyde and 2-aminobenzoic acid and obtained the double-layer eight-core lanthanide clusters [Dy8(μ3-OH)6(L5)2(L6)8] (3) and [Gd8(μ3-OH)6(L5)2(L6)8]·4CH3OH·CH3CN (4). The upper and lower layers of cluster 3 have four metal ions, respectively, forming a huge cavity inside the structure. This is the first time that a multinuclear lanthanide cluster with a layered structure has been constructed by the in situ reaction of mixed ligands. AC susceptibility test shows that the imaginary part signals of cluster 1 do not show frequency dependence and the imaginary part signals of cluster 3 show frequency dependence at low temperatures. By fitting the Arrhenius equation, we obtain Ueff = 2.87 K and τ0 = 2.76 × 10–4 s. 

Manipulation of Mixed Ligands to Form Single-Layer and Double-Layer Lanthanide Clusters and Their Magnetic Properties

Preparation and Purification of Endohedral Metallofullerenes

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