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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.
Strong and ductile high temperature soft magnets through Widmanstätten precipitates
Fast growth of sustainable energy production requires massive electrification of transport, industry and households, with electrical motors as key components. These need soft magnets with high saturation magnetization, mechanical strength, and thermal stability to operate efficiently and safely. Reconciling these properties in one material is challenging because thermally-stable microstructures for strength increase conflict with magnetic performance. Here, we present a material concept that combines thermal stability, soft magnetic response, and high mechanical strength. The strong and ductile soft ferromagnet is realized as a multicomponent alloy in which precipitates with a large aspect ratio form a Widmanstätten pattern. The material shows excellent magnetic and mechanical properties at high temperatures while the reference alloy with identical composition devoid of precipitates significantly loses its magnetization and strength at identical temperatures. The work provides a new avenue to develop soft magnets for high-temperature applications, enabling efficient use of sustainable electrical energy under harsh operating conditions.
Intermolecular charge transfer enhances the performance of molecular rectifiers
Molecular-scale diodes made from self-assembled monolayers (SAMs) could complement silicon-based technologies with smaller, cheaper, and more versatile devices. However, advancement of this emerging technology is limited by insufficient electronic performance exhibited by the molecular current rectifiers. We overcome this barrier by exploiting the charge-transfer state that results from co-assembling SAMs of molecules with strong electron donor and acceptor termini. We obtain a substantial enhancement in current rectification, which correlates with the degree of charge transfer, as confirmed by several complementary techniques. These findings provide a previously enexplored method for manipulating the properties of molecular electronic devices by exploiting donor/acceptor interactions. They also serve as a model test platform for the study of doping mechanisms in organic systems. Our devices have the potential for fast widespread adoption due to their low-cost processing and self-assembly onto silicon substrates, which could allow seamless integration with current technologies.
Elucidating Structure Formation in Highly Oriented Triple Cation Perovskite Films
Metal halide perovskites are an emerging class of crystalline semiconductors of great interest for application in optoelectronics. Their properties are dictated not only by their composition, but also by their crystalline structure and microstructure. While significant efforts are dedicated to the development of strategies for microstructural control, significantly less is known about the processes that govern the formation of their crystalline structure in thin films, in particular in the context of crystalline orientation. This work investigates the formation of highly oriented triple cation perovskite films fabricated by utilizing a range of alcohols as an antisolvent. Examining the film formation by in situ grazing-incidence wide-angle X-ray scattering reveals the presence of a short-lived highly oriented crystalline intermediate, which is identified as FAI-PbI2-xDMSO. The intermediate phase templates the crystallization of the perovskite layer, resulting in highly oriented perovskite layers. The formation of this dimethylsulfoxide (DMSO) containing intermediate is triggered by the selective removal of N,N-dimethylformamide (DMF) when alcohols are used as an antisolvent, consequently leading to differing degrees of orientation depending on the antisolvent properties. Finally, this work demonstrates that photovoltaic devices fabricated from the highly oriented films, are superior to those with a random polycrystalline structure in terms of both performance and stability.
Resonating holes vs molecular spin-orbit coupled states in group-5 lacunar spinels
The valence electronic structure of magnetic centers is one of the factors that determines the characteristics of a magnet. This may refer to orbital degeneracy, as for jeff = 1/2 Kitaev magnets, or near-degeneracy, e.g., involving the third and fourth shells in cuprate superconductors. Here we explore the inner structure of magnetic moments in group-5 lacunar spinels, fascinating materials featuring multisite magnetic units in the form of tetrahedral tetramers. Our quantum chemical analysis reveals a very colorful landscape, much richer than the single-electron, single-configuration description applied so far to all group-5 GaM4X8 chalcogenides, and clarifies the basic multiorbital correlations on M4 tetrahedral clusters: while for V strong correlations yield a wave-function that can be well described in terms of four V4+V3+V3+V3+ resonant valence structures, for Nb and Ta a picture of dressed molecular-orbital jeff = 3/2 entities is more appropriate. These internal degrees of freedom likely shape vibronic couplings, phase transitions, and the magneto-electric properties in each of these systems.
Probing magnetic properties at the nanoscale: in-situ Hall measurements in a TEM
We report on advanced in-situ magneto-transport measurements in a transmission electron microscope. The approach allows for concurrent magnetic imaging and high resolution structural and chemical characterization of the same sample. Proof-of-principle in-situ Hall measurements on presumably undemanding nickel thin films supported by micromagnetic simulations reveal that in samples with non-trivial structures and/or compositions, detailed knowledge of the latter is indispensable for a thorough understanding and reliable interpretation of the magneto-transport data. The proposed in-situ approach is thus expected to contribute to a better understanding of the Hall signatures in more complex magnetic textures.
Calorimetric evidence for two phase transitions in Ba1−xKxFe2As2 with fermion pairing and quadrupling states
Materials that break multiple symmetries allow the formation of four-fermion condensates above the superconducting critical temperature (T c). Such states can be stabilized by phase fluctuations. Recently, a fermionic quadrupling condensate that breaks the Z 2 time-reversal symmetry was reported in Ba1−xKxFe2As2. A phase transition to the new state of matter should be accompanied by a specific heat anomaly at the critical temperature where Z 2 time-reversal symmetry is broken (TcZ2>Tc). Here, we report on detecting two anomalies in the specific heat of Ba1−xKxFe2As2 at zero magnetic field. The anomaly at the higher temperature is accompanied by the appearance of a spontaneous Nernst effect, indicating the breakdown of Z 2 symmetry. The second anomaly at the lower temperature coincides with the transition to a zero-resistance state, indicating the onset of superconductivity. Our data provide the first example of the appearance of a specific heat anomaly above the superconducting phase transition associated with the broken time-reversal symmetry due to the formation of the novel fermion order.
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.