ESR study of the spin ladder with uniform Dzyaloshinskii-Moria interaction

Evolution of the ESR absorption in a strong-leg spin ladder magnet (C$_7$H$_{10}$N$_2$)$_2$CuBr$_4$ (abbreviated as DIMPY) is studied from 300K to 400mK. Temperature dependence of the ESR relaxation follows a staircase of crossovers between different relaxation regimes. We ague that the main mechanism of ESR line broadening in DIMPY is uniform Dzyaloshinskii-Moria interaction ($|\vec{D}|=0.20$K) with an effective longitudinal component along an exchange bond of Cu ions within the legs resulting from the low crystal symmetry of DIMPY and nontrivial orbital ordering. The same Dzyaloshinskii-Moriya interaction results in the lifting of the triplet excitation degeneracy, revealed through the weak splitting of the ESR absorption at low temperatures.Comment: 13 pages, submitted to PRB, Fig.3 update

Temperature dependence of EPR linewidth in one-dimensional magnets: A quasi-classical approach

An analytical expression for the EPR linewidth of an exchange-coupled 1/2-spin chain originating from uniform Dzyaloshinskii-Moriya interaction is derived using a quasi-classical approach. The expression successfully reproduces the results obtained by numerical quantum mechanical calculations based on Green's function method at T > 2J/k B. © 2013 Allerton Press, Inc

Possible mechanisms of magnon sidebands formation in transition metal compounds

In this short report possible mechanisms of magnon sidebands formation in transition metal compounds are shortly discussed. Besides the well known exchange electric dipole mechanism, suggested by Tanabe, Moriya and Sugano, recently a new the exciton-magnon absorption mechanisms assisted by phonons become actual. Special attention is paid to possible contribution of phonon-assisted electric dipole exchange transition in quasi-one-dimensional antiferromagnet KCUF 3

Spin correlations and Dzyaloshinskii-Moriya interaction in Cs2_2CuCl4_4

We report on electron spin resonance (ESR) studies of the spin relaxation in Cs$_2$CuCl$_4$. The main source of the ESR linewidth at temperatures $T \leq 150$ K is attributed to the uniform Dzyaloshinskii-Moriya interaction. The vector components of the Dzyaloshinskii-Moriya interaction are determined from the angular dependence of the ESR spectra using a high-temperature approximation. Both the angular and temperature dependence of the ESR linewidth have been analyzed using a self-consistent quantum-mechanical approach. In addition analytical expressions based on a quasi-classical picture for spin fluctuations are derived, which show good agreement with the quantum-approach for temperatures $T \geq 2J/k_{\rm B} \approx 15$ K. A small modulation of the ESR linewidth observed in the $ac$-plane is attributed to the anisotropic Zeeman interaction, which reflects the two magnetically nonequivalent Cu positions

Energy level diagram, wavefunctions, and probabilities of optical transitions in KCuF 3

Using modern concepts of the crystal field in ion-covalent compounds, we calculate the energy level diagram, wavefunctions, and probabilities of optical transitions in the orbital ordering phase of KCuF 3. On this basis, we discuss the possible mechanisms by which an optical absorption sideband structure forms, accompanied by the creation of magnons. © Pleiades Publishing, Ltd., 2011

Cobalt Complexes of Bulky PNP Ligand: H2 Activation and Catalytic Two-Electron Reactivity in Hydrogenation of Alkenes and Alkynes

The reactivity of cobalt pincer complexes supported by the bulky tetramethylated PNP ligands Me4PNPR(R = iPr, tBu) has been investigated. In these ligands, the undesired H atom loss reactivity observed earlier in some classical CH2-arm PNP cobalt complexes is blocked, allowing them to be utilized for promoting two-electron catalytic transformations at the cobalt center. Accordingly, reaction of the formally CoIMe complex 3 with H2 under ambient pressure and temperature afforded the CoIII trihydride 4-H, in a reaction cascade reasoned to proceed by two-electron oxidative addition and reductive eliminations. This mechanistic proposal, alongside the observance of alkene insertion and ethane production upon sequential exposure of 3 to ethylene and H2, prompted an exploration into 3 as a catalyst for hydrogenation. Complex 4-H, formed in situ from 3 under H2, was found to be active in the catalytic hydrogenation of alkenes and alkynes. The proposed two-electron mechanism is reminiscent of the platinum group metals and demonstrates the utility of the bulky redox-innocent Me4PNPR ligand in the avoidance of one-electron reactivity, a concept that may show broad applicability in expanding the scope of earth-abundant first-row transition-metal catalysis.journal articl

Transfer Hydrogenation of Carbonyl Groups, Imines and N‐Heterocycles Catalyzed by Simple, Bipyridine‐Based MnI Complexes

Utilization of hydroxy‐substituted bipyridine ligands in transition metal catalysis mimicking [Fe]‐hydrogenase has been shown to be a promising approach in developing new catalysts for hydrogenation. For example, MnI complexes with 6,6′‐dihydroxy‐2,2′‐bipyridine ligand have been previously shown to be active catalysts for CO2 hydrogenation. In this work, simple bipyridine‐based Mn catalysts were developed that act as active catalysts for transfer hydrogenation of ketones, aldehydes and imines. For the first time, Mn‐catalyzed transfer hydrogenation of N ‐heterocycles was reported. The highest catalytic activity among complexes with variously substituted ligands was observed for the complex bearing two OH groups in bipyridine. Deuterium labeling experiments suggest a monohydride pathway

Stent-Graft Treatment of Anterior Interventricular Artery Extravasation Type IIICS: a Clinical Case

Background. Every percutaneous coronary intervention (PCI) is potentially causative of severe surgical accidents. Routine manipulations with catheters, guidewire, delivery systems or stents can damage vascular walls leading to immediate complications like extravasation. In interventional cardiology, ruptures occur in 0.19–0.93% of PCI cases. The endovascular surgeon is to immediately react in case of an accident and decide on further action to  repair the coronary artery rupture.Materials and methods. The article describes a clinical case of a PCI complication, extravasation type IIICS, during a routine stenting of anterior interventricular artery. Stent­grafting at rapture was decided upon conclusive analysis of the situation.Results and discussion. A percutaneous coronary intervention, including routine surgery, potentially poses diverse complications. Extravasation is an expectable complication type. The endovascular surgeon must be sufficiently experienced to decide on an appropriate tactics. The outcome of stent­graft implantation was satisfactory.Conclusion. Stent­graft placement may be a method of choice in a PCI complication of surgery like extravasation type IIICS

Proton-responsive naphthyridinone-based RuII complexes and their reactivity with water and alcohols

We report the synthesis and reactivity of RuII complexes with a new naphthyridinone-substituted phosphine ligand, 7-(diisopropylphosphinomethyl)-1,8-naphthyridin-2(1H)-one (L-H), which contains two reactive sites that can potentially be deprotonated by a strong base: an NH proton of naphthyridinone and a methylene arm attached to the phosphine. In the absence of a base, the stable bis-ligated complex Ru(L-H)2Cl2 (1) containing two NH groups in the secondary coordination sphere is formed. Upon further reaction with a base, a doubly deprotonated, dimeric complex is obtained, [Ru2(L*-H)2(L)2] (2), in which two of the four ligands undergo deprotonation at the NH (L), while the other two ligands are deprotonated at the methylene groups (L*-H) as confirmed by an X-ray diffraction study; intramolecular hydrogen bonding is present between the NH group of one ligand and an O-atom of another ligand in the dimeric structure, which stabilizes the observed geometry of the complex. Complex 2 reacts with protic solvents such as water or methanol generating aqua Ru(L)2(OH2)2 (3) or methanol complexes Ru(L)2(MeOH)2 (4), respectively, both exhibiting intramolecular H-bonded patterns with surrounding ligands at least in the solid state. These complexes react with benzyl alcohols to give aldehydes via base-free acceptorless dehydrogenation