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.
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.
Vascular restenosis after balloon dilation is largely caused by the over‐proliferation of smooth muscle cells, which is triggered and exacerbated by local excessive inflammation and oxidative stress. ...The excessive inflammatory and oxidative stress cause tissue/cell damage, hamper endothelial functions, and worsen intimal hyperplasia and restenosis. A high level of reactive oxygen species (ROS) overproduction is regarded as the main culprit. Therefore, efficiently inhibiting ROS over‐production or weightily depleting them is of great significance. Herein, a “ROS‐responsive/scavenging prodrug” is introduced into balloon coating for the treatment of vascular restenosis. A reversible phenylboronic ester‐bearing caffeic acid (CA) macromolecular prodrug (PBC) is designed for the controlled and on‐demand dual‐drug release triggered by the local high ROS level; the released CA and 4‐hydroxybenzyl alcohol exhibit efficient antioxidant and anti‐inflammatory effects by scavenging ROS, thereby regulating vascular microenvironment and protecting endothelium functions. To accelerate endothelium regeneration, pro‐endothelial microRNA‐126 is further introduced. The ROS‐responsive/scavenging prodrug/miRNA balloon coating efficiently prevents intimal hyperplasia, alleviates local inflammation, and improves endothelium healing in a rat abdominal aorta restenosis model, which may provide applicative perspectives for next‐generation drug‐coated balloons and other cardiovascular diseases treatment.
A reversible phenylboronic ester‐bearing caffeic acid (CA) macromolecular prodrug (PBC) is designed for the controlled and on‐demand dual‐antioxidant release (CA and 4‐hydroxybenzyl alcohol (HBA)) triggered by the local high reactive oxygen species (ROS) level, thereby exhibiting antioxidant and anti‐inflammatory effects; the pro‐endothelial microRNA‐126 is introduced to further accelerate endothelialization. This ROS‐responsive/scavenging prodrug/miRNA balloon coating efficiently inhibits long‐term vascular restenosis.
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.
The synthesis, structure and magnetic properties of the indigo-bridged dilanthanide complexes {(η
-Cp*)
Ln}
(μ-ind)
with Ln = Gd or Dy and n = 0, 1 or 2 are described. The gadolinium complexes with n ...= 0 and 2 show typically weak exchange coupling, whereas the complex bridged by the radical ind
ligand shows an unusually large coupling constant of J = -11 cm
(-2J formalism). The dysprosium complexes with n = 0 and 1 are single-molecule magnets in zero applied field, whereas the complex with n = 2 does not show slow magnetic relaxation.
•The cryogenic magnetocaloric effect in different magnetic systems is discussed.•The assembly strategies toward 3d-, 4f- and 3d–4f based molecular magnetic coolants are described.•The recent advance ...in cryogenic molecular magnetic coolants is summarized.•The different nature of 3d and 4f ions must be considered in the design of molecular magnetic coolants.
This review outlines recent advances in the design of 3d-, 4f-, and 3d–4f type magnetic molecules for use as excellent cryogenic magnetic coolants based on the magnetocaloric effect (MCE), and the structure-magnetocaloric correlations of reported molecular coolants. Further improvements in the MCE values of molecular magnetic materials are also proposed based on assembly strategies from molecular chemistry and crystal engineering.
Adding small molecular plasticizers is the most common route to tailor the stretchability of poly(vinyl alcohol) (PVA). However, how the plasticization along with the nature of the plasticizer ...governs the structural homogeneity during stretching remains an open question to answer. Herein, two representative plasticizers, glycerol (GLY) and water, are chosen to endow the PVA films with ductility. It is found that large strain cavitations cause obvious stress whitening in the PVA/H2O films; on the contrary, most of the PVA/GLY films maintain transparent undergoing tensile deformation. Through a combination of experimental inspections and molecular dynamic simulation, it is revealed that partial water molecules that behave as free water will aggregate into microdomains, which serve as mechanical defects responsible for yielding voids. Whereas, the GLY plasticizer homogeneously disperses at a molecular level and interacts with PVA chains through strong hydrogen bonds. More interestingly, it is illustrated that the dispersion and bound states of plasticizers are closely related to the mechanical character of the plasticized PVA films. These findings offer new insight into the working mechanism of plasticization on the structural stability during stretching, and guide the design of PVA/plasticizer system to obtain excellent comprehensive mechanics.
The structural stability of plasticized PVA films during stretching strongly relies on the dispersion and bound states of plasticizers. A molecule‐level dispersion of glycerol and its tight interaction with PVA chains endow the PVA film with a facile reformation of H‐bonds after breakage. Whereas, freezable bound water and free water aggregate into microdomains responsible for forming cavitations.
Hydrogen bonds (H-bonds) in poly(vinyl alcohol) (PVA) play a crucial role in macroscopic mechanical properties, particularly for stretchability. However, there is still some ambiguity about the ...quantitative dependence of H-bond interactions on the mechanical performance, mainly attributed to the difficulty in the discrimination of various H-bond types. Herein, small molecular chemicals as plasticizers were incorporated into the PVA matrix to tailor the H-bonding interactions. By altering the PVA molecular weight, plasticizer type and loading, both the stretchability and H-bond content were regulated on a large scale. By a combination of DMA, IR spectroscopy, MD simulation and solid-state
13
C-NMR, every sort of H-bond in PVA was assigned, and their relative fractions were ascertained quantitatively. After correlating the elongation ratio with the relative fraction of the different types of H-bonding interaction, it was found that all the pairs of elongation
vs.
intermolecular H-bond content derived from different series of PVA/plasticizer films could be plotted into a master curve and exhibited good linearity, indicating that intermolecular H-bonds dominate the mechanical stretchability in PVA films. Our efforts contribute towards an in-depth understanding of performance optimization induced by H-bond manipulation from empirical, phenomenological aspects to intrinsic, numerical insights.
For all the PVA/plasticizer films, a good linearity exists between elongations and intermolecular H-bonds as ascertained by solid-state
13
C NMR.
Permanent pacemakers are used for symptomatic bradycardia and biventricular pacing (BVP)‐cardiac resynchronization therapy (BVP‐CRT) is established for heart failure (HF) patients traditionally. ...According to guidelines, patients’ selection for CRT is based on QRS duration (QRSd) and morphology by surface electrocardiogram (ECG). Cardiovascular imaging techniques evaluate cardiac structure and function as well as identify pathophysiological substrate changes including the presence of scar. Cardiovascular imaging helps by improving the selection of candidates, guiding left ventricular (LV) lead placement, and optimization devices during the follow‐up. Conduction system pacing (CSP) includes His bundle pacing (HBP) and left bundle branch pacing (LBBP) which is screwed into the interventricular septum. CSP maintains and restores ventricular synchrony in patients with native narrow QRSd and left bundle branch block (LBBB), respectively. LBBP is more feasible than HBP due to a wider target area. This review highlights the role of multimodality cardiovascular imaging including fluoroscopy, echocardiography, cardiac magnetic resonance (CMR), myocardial scintigraphy, and computed tomography (CT) in the pre‐procedure assessment for CSP, better selection for CSP candidates, the guidance of CSP lead implantation, and the optimization of devices programming after the procedure. We also compare the different characteristics of multimodality imaging and discuss their potential roles in future CSP implantation.
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