Capturing Unstable Metallofullerenes

Metallofullerenes are interesting molecules with unique structures and physicochemical properties. After they are formed in the arc-discharge process, they are first buried in the carbon soot, which requires solvent extraction to fish them out, normally followed by HPLC separation. In this minireview, we summarize the main procedures developed to obtain pure metallofullerenes, including well-established extraction with conventional fullerene solvents followed by HPLC (procedure (I) as well as several methods developed for isolation and purification of unstable fullerenes insoluble in conventional fullerene solvents, including chemical modification followed by dissolution (II.1), chemical functionalization during extraction followed by HPLC (II.2), and chemical functionalization of ionic EMFs after redox-extraction followed by HPLC (procedure II.3). The main focus here is on procedure II.3, for which the current status and future perspective are discussed

Nd─Nd Bond in Ih and D5h Cage Isomers of Nd2@C80 Stabilized by Electrophilic CF3 Addition

Synthesis of molecular compounds with metal–metal bonds between 4f elements is recognized as one of the fascinating milestones in lanthanide metallochemistry. The main focus of such studies is on heavy lanthanides due to the interest in their magnetism, while bonding between light lanthanides remains unexplored. In this work, the Nd─Nd bonding in Nd-dimetallofullerenes as a case study of metal–metal bonding between early lanthanides is demonstrated. Combined experimental and computational study proves that pristine Nd2@C80 has an open shell structure with a single electron occupying the Nd─Nd bonding orbital. Nd2@C80 is stabilized by a one-electron reduction and further by the electrophilic CF3 addition to [Nd2@C80]−. Single-crystal X-ray diffraction reveals the formation of two Nd2@C80(CF3) isomers with D5h-C80 and Ih-C80 carbon cages, both featuring a single-electron Nd─Nd bond with the length of 3.78–3.79 Å. The mutual influence of the exohedral CF3 group and endohedral metal dimer in determining the molecular structure of the adducts is analyzed. Unlike Tb or Dy analogs, which are strong single-molecule magnets with high blocking temperature of magnetization, the slow relaxation of magnetization in Nd2@Ih-C80(CF3) is detectable via out-of-phase magnetic susceptibility only below 3 K and in the presence of magnetic field

Single-Electron Lanthanide-Lanthanide Bonds Inside Fullerenes toward Robust Redox-Active Molecular Magnets

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. © 2019 American Chemical Society

Helical Nanographenes Containing an Azulene Unit : Synthesis, Crystal Structures, and Properties

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. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

Directed exciton transport highways in organic semiconductors

Exciton bandwidths and exciton transport are difficult to control by material design. We showcase the intriguing excitonic properties in an organic semiconductor material with specifically tailored functional groups, in which extremely broad exciton bands in the near-infrared-visible part of the electromagnetic spectrum are observed by electron energy loss spectroscopy and theoretically explained by a close contact between tightly packing molecules and by their strong interactions. This is induced by the donor–acceptor type molecular structure and its resulting crystal packing, which induces a remarkable anisotropy that should lead to a strongly directed transport of excitons. The observations and detailed understanding of the results yield blueprints for the design of molecular structures in which similar molecular features might be used to further explore the tunability of excitonic bands and pave a way for organic materials with strongly enhanced transport and built-in control of the propagation direction

Carbon cage isomers and magnetic Dy⋯Dy interactions in Dy2O@C88 and Dy2C2@C88 metallofullerenes

Three isomers of Dy2O@C88 and two isomers of Dy2C2@C88 were synthesized and structurally characterized by single-crystal X-ray diffraction, vibrational spectroscopy, and DFT calculations. Both types of clusterfullerenes feature 4-fold electron transfer to the carbon cage, thus resulting in the same carbon cage isomers identified as C1(26), Cs(32), and D2(35). The studies of Dy⋯Dy superexchange interactions in Dy2O and Dy2C2 clusters revealed that the O2− bridge favors antiferromagnetic coupling whereas the acetylide group C22− supports ferromagnetic coupling of Dy magnetic moments. The strength of the coupling showed a considerable variability in different cage isomers. All metallofullerenes exhibited slow relaxation of magnetization and magnetic hysteresis. In Dy2O@C88 isomers the hysteresis remained open up to 7-9 K, while in Dy2C2@C88 the hysteresis loops were closed already at 2.5 K. This study demonstrated that both the endohedral bridge between metal atoms and the fullerene cage play an important role in magnetic interactions and relaxation of magnetization

Tailoring Magnetic Features in Zigzag-Edged Nanographenes by Controlled Diels–Alder Reactions

Nanographenes (NGs) with tunable electronic and magnetic properties have attracted enormous attention in the realm of carbon-based nanoelectronics. In particular, NGs with biradical character at the ground state are promising building units for molecular spintronics. However, most of the biradicaloids are susceptible to oxidation under ambient conditions and photolytic degradation, which hamper their further applications. Herein, we demonstrated the feasibility of tuning the magnetic properties of zigzag-edged NGs in order to enhance their stability via the controlled Diels–Alder reactions of peri-tetracene (4-PA). The unstable 4-PA (y0=0.72; half-life, t1/2=3 h) was transformed into the unprecedented benzo-peri-tetracenes (BPTs) by a one-side Diels–Alder reaction, which featured a biradical character at the ground state (y0=0.60) and exhibited remarkable stability under ambient conditions for several months. In addition, the fully zigzag-edged circumanthracenes (CAs) were achieved by two-fold or stepwise Diels–Alder reactions of 4-PA, in which the magnetic properties could be controlled by employing the corresponding dienophiles. Our work reported herein opens avenues for the synthesis of novel zigzag-edged NGs with tailor-made magnetic properties. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinhei

Inferring the Dy-N axis orientation in adsorbed DySc2_2N@C80_{80} endofullerenes by linearly polarized x-ray absorption spectroscopy

Endofullerene DySc$_2$N@C$_{80}$ is a single-molecule magnet with a large magnetic anisotropy and high blocking temperature, which is promising for nanomagnetic applications. As the easy axis of magnetization coincides with the Dy-N bond direction, it is important to understand the structure of the DySc$_2$N unit in the fullerene cage and to control the orientation of the molecules. Here we report on the experimental determination of Dy-N axis by x-ray absorption spectroscopy (XAS) with linear polarized light at the Dy−M$_{4,5}$ white lines. DySc$_2$N@C$_{80}$ molecules were adsorbed on a Pt(111) surface and XAS was performed as a function of temperature in the range between 35 and 300 K. The M$_5$/M$_4$ branching ratio shows a clear and reversible variation with temperature which can be explained, on the basis of a thermodynamic model, by a change of average orientation of the molecules with temperature. The XAS spectra are well reproduced by ligand field multiplet calculations. It is shown that the angle between the magnetization (Dy-N) axis and the surface plane can be directly inferred from the XAS spectra with in-plane polarization by comparison with calculated spectra. It is found that the endohedral unit is randomly oriented at room temperature but tends towards orientation parallel to the surface at low temperature, indicating a weak but non-negligible interaction between the endohedral units and the metal surface

Using internal strain and mass to modulate Dy⋯Dy coupling and relaxation of magnetization in heterobimetallic metallofullerenes DyM2N@C80 and Dy2MN@C80 (M = Sc, Y, La, Lu)

Endohedral clusters inside metallofullerenes experience considerable inner strain when the size of the hosting cage is comparably small. This strain can be tuned in mixed-metal metallofullerenes by combining metals of different sizes. Here we demonstrate that the internal strain and mass can be used as variables to control Dy⋯Dy coupling and relaxation of magnetization in Dy-metallofullerenes. Mixed-metal nitride clusterfullerenes DyxY3−xN@Ih-C80 (x = 0-3) and Dy2LaN@Ih-C80 combining Dy with diamagnetic rare-earth elements, Y and La, were synthesized and characterized by single-crystal X-ray diffraction, SQUID magnetometry, ab initio calculations, and spectroscopic techniques. DyxY3−xN clusters showed a planar structure, but the slightly larger size of Dy3+ in comparison with that of Y3+ resulted in increased elongation of the nitrogen thermal ellipsoid, showing enhancement of the out-of-plane vibrational amplitude. When Dy was combined with larger La, the Dy2LaN cluster appeared strongly pyramidal with the distance between two nitrogen sites of 1.15(1) Å, whereas DyLa2N@C80 could not be obtained in a separable yield. Magnetic studies revealed that the relaxation of magnetization and blocking temperature of magnetization in the DyM2N@C80 series (M = Sc, Y, Lu) correlated with the mass of M, with DySc2N@C80 showing the fastest and DyLu2N@C80 the slowest relaxation. Ab initio calculations predicted very similar g-tensors for Dy3+ ground state pseudospin in all studied DyM2N@C80 molecules, suggesting that the variation in relaxation is caused by different vibrational spectra of these compounds. In the Dy2MN@C80 series (M = Sc, Y, La, Lu), the magnetic and hysteretic behavior was found to correlate with Dy⋯Dy coupling, which in turn appears to depend on the size of M3+. Across the Dy2MN@C80 series, the energy difference between ferromagnetic and antiferromagnetic states changes from 5.6 cm−1 in Dy2ScN@C80 to 3.0 cm−1 in Dy2LuN@C80, 1.0 cm−1 in Dy2YN@C80, and −0.8 cm−1 in Dy2LaN@C80. The coupling of Dy ions suppresses the zero-field quantum tunnelling of magnetization but opens new relaxation channels, making the relaxation rate dependent on the coupling strengths. DyY2N@C80 and Dy2YN@C80 were found to be non-luminescent, while the luminescence reported for DyY2N@C80 was caused by traces of Y3N@C80 and Y2ScN@C8

Optical Anisotropy and Momentum-Dependent Excitons in Dibenzopentacene Single Crystals

High-quality single crystals of the organic semiconductor (1,2;8,9)-dibenzopentacene were grown via physical vapor transport. The crystal structure─unknown before─was determined by single-crystal X-ray diffraction; polarization-dependent optical absorption measurements display a large anisotropy in the ac plane of the crystals. The overall Davydov splitting is ∼110 meV, which is slightly lower than that in the close relative pentacene (120 meV). Momentum-dependent electron energy-loss spectroscopy measurements show a clear exciton dispersion of the Davydov components. An analysis of the dispersion using a simple 1D model indicates smaller electron- and hole-transfer integrals in dibenzopentacene as compared to pentacene. The spectral weight distribution of the excitation spectra is strongly momentum-dependent and demonstrates a strong momentum-dependent admixture of Frenkel excitons, charge-transfer excitons, and vibrational modes