Single-molecule magnets (SMMs) containing only one metal center may represent the lower size limit for molecule-based magnetic information storage materials. Their current drawback is that all SMMs ...require liquid-helium cooling to show magnetic memory effects. We now report a chemical strategy to access the dysprosium metallocene cation (Cp
)Dy(Cp*)
(Cp
, penta-iso-propylcyclopentadienyl; Cp
pentamethylcyclopentadienyl), which displays magnetic hysteresis above liquid-nitrogen temperatures. An effective energy barrier to reversal of the magnetization of
= 1541 wave number is also measured. The magnetic blocking temperature of
= 80 kelvin for this cation overcomes an essential barrier toward the development of nanomagnet devices that function at practical temperatures.
ion of a chloride ligand from the dysprosium metallocene (Cpttt)2DyCl (1Dy Cpttt=1,2,4‐tri(tert‐butyl)cyclopentadienide) by the triethylsilylium cation produces the first base‐free rare‐earth ...metallocenium cation (Cpttt)2Dy+ (2Dy) as a salt of the non‐coordinating B(C6F5)4− anion. Magnetic measurements reveal that 2DyB(C6F5)4 is an SMM with a record anisotropy barrier up to 1277 cm−1 (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of 2Dy is further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low‐lying Kramers doublets correspond to a well‐defined MJ value, with no significant mixing even in the higher doublets.
SMMashing: A dysprosium(III) metallocenium cation is a single‐molecule magnet (SMM) with a record anisotropy barrier of 1277 cm−1 and record magnetic blocking up to 60 K, including hysteresis with coercivity.
Discrimination of physically similar molecules by porous solids represents an important yet challenging task in industrially relevant chemical separations. Precisely controlled pore dimension and/or ...tailored pore surface functionality are crucial to achieve high‐efficiency separation. Metal‐organic frameworks (MOFs) are promising candidates for these challenging separations in light of their structural diversity as well as highly adjustable pore dimension/functionality. We report here a microporous, ftw‐type Zr‐based MOF structure, HIAM‐410 (HIAM=Hoffmann Institute of Advanced Materials), built on hexanuclear Zr6 cluster and pyrene‐1,3,6,8‐tetracarboxylate (ptc4−). Its crystallographic structure has been determined using continuous rotation electron diffraction (cRED) technique combined with Rietveld refinement against powder X‐ray diffraction data, aided by low‐dose high‐resolution transmission electron microscopy (HRTEM) imaging. The compound features exceptional framework stability that is comparable to the prototype MOF UiO‐66. Interestingly, the linker vacancies in the pristine MOF structure could be partially restored by post‐synthetic linker insertion. Its separation capability of hexane isomers is enhanced substantially upon the linker vacancy engineering. The restored structure exhibits efficient splitting of monobranched and dibranched hexane isomers at both room temperature and industrially relevant temperature.
A highly robust ftw‐type zirconium‐based metal–organic framework has been constructed. Its linker vacancy sites are restored by post‐synthetic linker insertion, which notably enhances its separation performance toward alkane isomers.
By using transitionless quantum driving algorithm (TQDA), we present an efficient scheme for the shortcuts to the holonomic quantum computation (HQC). It works in decoherence-free subspace (DFS) and ...the adiabatic process can be speeded up in the shortest possible time. More interestingly, we give a physical implementation for our shortcuts to HQC with nitrogen-vacancy centers in diamonds dispersively coupled to a whispering-gallery mode microsphere cavity. It can be efficiently realized by controlling appropriately the frequencies of the external laser pulses. Also, our scheme has good scalability with more qubits. Different from previous works, we first use TQDA to realize a universal HQC in DFS, including not only two noncommuting accelerated single-qubit holonomic gates but also a accelerated two-qubit holonomic controlled-phase gate, which provides the necessary shortcuts for the complete set of gates required for universal quantum computation. Moreover, our experimentally realizable shortcuts require only two-body interactions, not four-body ones, and they work in the dispersive regime, which relax greatly the difficulty of their physical implementation in experiment. Our numerical calculations show that the present scheme is robust against decoherence with current experimental parameters.
Reduction of the uranium(III) metallocene (η5‐C5iPr5)2UI (1) with potassium graphite produces the “second‐generation” uranocene (η5‐C5iPr5)2U (2), which contains uranium in the formal divalent ...oxidation state. The geometry of 2 is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground‐state valence electron configuration of uranium(II) revealed by electronic spectroscopy and density functional theory to be 5f3 6d1. Appreciable covalent contributions to the metal‐ligand bonds were determined from a computational study of 2, including participation from the uranium 5f and 6d orbitals. Whereas three unpaired electrons in 2 occupy orbitals with essentially pure 5f character, the fourth electron resides in an orbital defined by strong 7s‐6dz2
mixing.
A new generation: Reduction of the uranium(III) metallocene (η5‐C5iPr5)2UI with potassium graphite produces the “second‐generation” uranocene (η5‐C5iPr5)2U, which contains uranium in the formal divalent oxidation state. The geometry of (η5‐C5iPr5)2U is that of a perfectly linear bis(cyclopentadienyl) sandwich complex.
Conspectus The discovery of materials capable of storing magnetic information at the level of single molecules and even single atoms has fueled renewed interest in the slow magnetic relaxation ...properties of single-molecule magnets (SMMs). The lanthanide elements, especially dysprosium, continue to play a pivotal role in the development of potential nanoscale applications of SMMs, including, for example, in molecular spintronics and quantum computing. Aside from their fundamentally fascinating physics, the realization of functional materials based on SMMs requires significant scientific and technical challenges to be overcome. In particular, extremely low temperatures are needed to observe slow magnetic relaxation, and while many SMMs possess a measurable energy barrier to reversal of the magnetization (U eff), very few such materials display the important properties of magnetic hysteresis with remanence and coercivity. Werner-type coordination chemistry has been the dominant method used in the synthesis of lanthanide SMMs, and most of our knowledge and understanding of these materials is built on the many important contributions based on this approach. In contrast, lanthanide organometallic chemistry and lanthanide magnetochemistry have effectively evolved along separate lines, hence our goal was to promote a new direction in single-molecule magnetism by uniting the nonclassical organometallic synthetic approach with the traditionally distinct field of molecular magnetism. Over the last several years, our work on SMMs has focused on obtaining a detailed understanding of why magnetic materials based on the dysprosium metallocene cation building block {Cp2Dy}+ display slow magnetic relaxation. Specifically, we aspired to control the SMM properties using novel coordination chemistry in a way that hinges on key considerations, such as the strength and the symmetry of the crystal field. In establishing that the two cyclopentadienyl ligands combine to provide a strongly axial crystal field, we were able to propose a robust magneto-structural correlation for understanding the properties of dysprosium metallocene SMMs. In doing so, a blueprint was established that allows U eff and the magnetic blocking temperature (T B) to be improved in a well-defined way. Although experimental discoveries with SMMs occur more rapidly than quantitative theory can (currently) process and explain, a clear message emanating from the literature is that a combination of the two approaches is most effective. In this Account, we summarize the main findings from our own work on dysprosium metallocene SMMs, and consider them in the light of related experimental studies and theoretical interpretations of related materials reported by other protagonists. In doing so, we aim to contribute to the nascent and healthy debate on the nature of spin dynamics in SMMs and allied molecular nanomagnets, which will be crucial for the further advancement of this vibrant research field.
Over the past few years, our understanding of hot accretion flows has been improved significantly by two findings: (i) only a small fraction of the accretion flow available at the outer boundary can ...finally fall on to the black hole, while most of it is lost in the outflow; (ii) electrons can directly receive a large fraction of the viscously dissipated energy in the accretion flow (i.e. δ ∼ 0.1-0.5). The radiative efficiency of the hot accretion flow when these two findings are taken into account has not yet been systematically studied, and this is the subject of our paper. We consider two regimes of the hot accretion model: advection-dominated accretion flows that lie in the regime of the low accretion rate, , and the luminous hot accretion flows (LHAFs) that lie above this accretion rate. For the LHAFs, we assume that the accretion flow has a two-phase structure above a certain accretion rate, and we adopt a simplification in our calculation of the dynamics. Our results indicate that the radiative efficiency of hot accretion flow increases with the accretion rate and that it is greatly enhanced by the direct viscous heating to electrons, compared to the previous case of δ ≪ 1. When the accretion rate is high, the radiative efficiency of the hot accretion flow is comparable to that of a standard thin disc. We present fitting formulae of radiative efficiency as a function of accretion rate for various values of δ.
Innovative synthetic coordination and, increasingly, organometallic chemistry are at the heart of advances in molecular magnetism. Smart ligand design is essential for implementing controlled ...modifications to the electronic structure and magnetic properties of transition metal and f-element compounds, and many important recent developments use nontraditional ligands based on low-coordinate main group elements to drive the field forward. This review charts progress in molecular magnetism from the perspective of ligands in which the donor atoms range from low-coordinate 2p elementsparticularly carbon but also boron and nitrogento the heavier p-block elements such as phosphorus, arsenic, antimony, and even bismuth. Emphasis is placed on the role played by novel main group ligands in addressing magnetic anisotropy of transition metal and f-element compounds, which underpins the development of single-molecule magnets (SMMs), a family of magnetic materials that can retain magnetization in the absence of a magnetic field below a blocking temperature. Nontraditional p-block donor atoms, with their relatively diffuse valence orbitals and more diverse bonding characteristics, also introduce scope for tuning the spin–orbit coupling properties and metal–ligand covalency in molecular magnets, which has implications in areas such as magnetic exchange coupling and spin crossover phenomena. The chemistry encompasses transition metals, lanthanides, and actinides and describes recently discovered molecular magnets that can be regarded, currently, as defining the state of the art. This review identifies that main group chemistry at the interface molecular magnetism is an area with huge potential to deliver new types of molecular magnets with previously unseen properties and applications.
Abstract
An important parameter in the theory of hot accretion flows around black holes is
δ
, which describes the fraction of “viscously” dissipated energy in the accretion flow that goes directly ...into heating electrons. For a given mass accretion rate, the radiative efficiency of a hot accretion flow is determined by
δ
. Unfortunately, the value of
δ
is hard to determine from first principles. The recent Event Horizon Telescope Collaboration (EHTC) results on M87* and Sgr A* provide us with a different way of constraining
δ
. By combining the mass accretion rates in M87* and Sgr A* estimated by the EHTC with the measured bolometric luminosities of the two sources, we derive good constraints on the radiative efficiencies of the respective accretion flows. In parallel, we use a theoretical model of hot magnetically arrested disks (MADs) to calculate the expected radiative efficiency as a function of
δ
(and accretion rate). By comparing the EHTC-derived radiative efficiencies with the theoretical results from MAD models, we find that Sgr A* requires
δ
≳ 0.3. A similar comparison in the case of M87* gives inconclusive results as there is still a large uncertainty in the accretion rate in this source.
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