Increasing the temperature at which molecules behave as single-molecule magnets is a serious challenge in molecular magnetism. One of the ways to address this problem is to create the molecules with strongly coupled lanthanide ions. In this work, endohedral metallofullerenes Y₂@C₈₀ and Dy₂@C₈₀ are obtained in the form of air-stable benzyl monoadducts. Both feature an unpaired electron trapped between metal ions, thus forming a single-electron metal-metal bond. Giant exchange interactions between lanthanide ions and the unpaired electron result in single-molecule magnetism of Dy₂@C₈₀(CH₂Ph) with a record-high 100 s blocking temperature of 18 K. All magnetic moments in Dy₂@C₈₀(CH₂Ph) are parallel and couple ferromagnetically to form a single spin unit of 21 μ_B with a dysprosium-electron exchange constant of 32 cm⁻¹. The barrier of the magnetization reversal of 613 K is assigned to the state in which the spin of one Dy centre is flipped.

Three unprecedented helical nanographenes (1, 2, and 3) containing an azulene unit are synthesized. The resultant helical structures are unambiguously confirmed by X‐ray crystallographic analysis. The embedded azulene unit in 2 possesses a record‐high twisting degree (16.1°) as a result of the contiguous steric repulsion at the helical inner rim. Structural analysis in combination with theoretical calculations reveals that these helical nanographenes manifest a global aromatic structure, while the inner azulene unit exhibits weak antiaromatic character. Furthermore, UV/Vis‐spectral measurements reveal that superhelicenes 2 and 3 possess narrow energy gaps (2: 1.88 eV; 3: 2.03 eV), as corroborated by cyclic voltammetry and supported by density functional theory (DFT) calculations. The stable oxidized and reduced states of 2 and 3 are characterized by in‐situ EPR/Vis–NIR spectroelectrochemistry. Our study provides a novel synthetic strategy for helical nanographenes containing azulene units as well as their associated structures and physical properties.

Engineering intramolecular exchange interactions between magnetic metal atoms is a ubiquitous strategy for designing molecular magnets. For lanthanides, the localized nature of 4f electrons usually results in weak exchange coupling. Mediating magnetic interactions between lanthanide ions via radical bridges is a fruitful strategy towards stronger coupling. In this work we explore the limiting case when the role of a radical bridge is played by a single unpaired electron. We synthesize an array of air-stable Ln₂@C₈₀(CH₂Ph) dimetallofullerenes (Ln₂ = Y₂, Gd₂, Tb₂, Dy₂, Ho₂, Er₂, TbY, TbGd) featuring a covalent lanthanide-lanthanide bond. The lanthanide spins are glued together by very strong exchange interactions between 4f moments and a single electron residing on the metal–metal bonding orbital. Tb₂@C₈₀(CH₂Ph) shows a gigantic coercivity of 8.2 Tesla at 5 K and a high 100-s blocking temperature of magnetization of 25.2 K. The Ln-Ln bonding orbital in Ln₂@C₈₀(CH₂Ph) is redox active, enabling electrochemical tuning of the magnetism.

A characteristic phenomenon of lanthanide–fullerene interactions is the transfer of metal valence electrons to the carbon cage. With early lanthanides such as La, a complete transfer of six valence electrons takes place for the metal dimers encapsulated in the fullerene cage. However, the low energy of the σ-type Ln–Ln bonding orbital in the second half of the lanthanide row limits the Ln₂ → fullerene transfer to only five electrons. One electron remains in the Ln–Ln bonding orbital, whereas the fullerene cage with a formal charge of −5 is left electron-deficient. Such Ln₂@C₈₀ molecules are unstable in the neutral form but can be stabilized by substitution of one carbon atom by nitrogen to give azafullerenes Ln₂@C₇₉N or by quenching the unpaired electron on the fullerene cage by reacting it with a chemical such as benzyl bromide, transforming one sp² carbon into an sp³ carbon and yielding the monoadduct Ln₂@C₈₀(CH₂Ph). Because of the presence of the Ln–Ln bonding molecular orbital with one electron, the Ln₂@C₇₉N and Ln₂@C₈₀(R) molecules feature a unique single-electron Ln–Ln bond and an unconventional +2.5 oxidation state of the lanthanides. In this Account, which brings together metallofullerenes, molecular magnets, and lanthanides in unconventional valence states, we review the progress in the studies of dimetallofullerenes with single-electron Ln–Ln bonds and highlight the consequences of the unpaired electron residing in the Ln–Ln bonding orbital for the magnetic interactions between Ln ions. Usually, Ln···Ln exchange coupling in polynuclear lanthanide compounds is weak because of the core nature of 4f electrons. However, when interactions between Ln centers are mediated by a radical bridge, stronger coupling may be achieved because of the diffuse nature of radical-based orbitals. Ultimately, when the role of a radical bridge is played by a single unpaired electron in the Ln–Ln bonding orbital, the strength of the exchange coupling is increased dramatically. Giant exchange coupling in endohedral Ln₂ dimers is combined with a rather strong axial ligand field exerted on the lanthanide ions by the fullerene cage and the excess electron density localized between two Ln ions. As a result, Ln₂@C₇₉N and Ln₂@C₈₀(CH₂Ph) compounds exhibit slow relaxation of magnetization and exceptionally high blocking temperatures for Ln = Dy and Tb. At low temperatures, the [Ln³⁺–e–Ln³⁺] fragment behaves as a single giant spin. Furthermore, the Ln–Ln bonding orbital in dimetallofullerenes is redox-active, which allows its population to be changed by electrochemical reactions, thus changing the magnetic properties because the change in the number of electrons residing in the Ln–Ln orbital affects the magnetic structure of the molecule.

Clusterfullerenes represent a novel branch of endohedral fullerenes, which are characterized by a robust fullerene cage with metal clusters encaged in its hollow. Since the discovery of nitride clusterfullerenes (NCFs) in 1999, the family of clusterfullerenes has been significantly expanded within the past decade, with new members including carbide clusterfullerenes (CCFs), hydrocarbide clusterfullerenes (HCCFs), oxide clusterfullerenes (OCFs), sulfide clusterfullerenes (SCFs), and carbonitride clusterfullerenes (CNCFs). We first present the classification of clusterfullerenes and list all the clusterfullerenes reported to date. For each type of clusterfullerenes, we review in detail their synthesis, separation, intriguing molecular structures and properties. For NCFs, as the first and most important clusterfullerenes, we point out the significance of their discovery and focus on their new synthesis and separation methods as well as the new advances. Finally the potential applications of clusterfullerenes are addressed. We conclude that clusterfullerenes appear to be the fastest growing family of endohedral fullerenes up to now, and emphasize the importance of exploring new structures and chemical functionalizations of clusterfullerenes.

Thermally-activated relaxation of the magnetization in the Dy-Sc nitride clusterfullerene Dy₂ScN@C₈₀-I_h proceeds via the fifth-excited Kramers doublet with the energy barrier of 1735 K.