Cd2FeReO6: A High-TC Double Perovskite Oxide with Remarkable Tunneling Magnetoresistance.

In this study, we successfully synthesized the double perovskite oxide Cd2FeReO6 by using a high-temperature and high-pressure method. The crystal structure was confirmed to belong to the P21/n space group, exhibiting approximately 68% ordering of Fe3+ and Re5+ ions at the perovskite B-site with the remaining regions showing antisite disorder. The measured Curie temperature of Cd2FeReO6 was 460 K, slightly lower than expected but still significantly above room temperature. Remarkably, Cd2FeReO6 displayed a remarkable low-field butterfly type tunneling magnetoresistance of -23% (-37% between the lowest and the largest values) at 5 K and 90 kOe, the highest among the A2FeReO6 (A = Ca, Sr, Pb, Ba) family. First-principles calculations provided insight into the origin of this observed magnetoresistance behavior, revealing Cd2FeReO6's half-metallic ferrimagnetic nature. This research extends our understanding of the double perovskite family and emphasizes its potential significance in the domains of spintronics and materials science. The exploration of differing magnetoresistance behaviors between Cd2FeReO6 and Ca2FeReO6, along with the influence of antisite disorder in Cd2FeReO6, opens intriguing avenues for further research.

Creation of a Field-Induced Co(II) Single-Ion Magnet by Doping into a Zn(II) Diamagnetic Metal-Organic Framework.

The combination of single-ion magnets (SIMs) and metal-organic frameworks (MOFs) is expected to produce new quantum materials. The principal issue to be solved in this regard is the development of new strategies for the synthesis of SIM-MOFs. This work demonstrates a new simple strategy for the synthesis of SIM-MOFs where a diamagnetic MOF is used as the framework into which the SIM sites are doped. 1, 0.5, and 0.2 mol% of the Co(II) ions are doped into the Zn(II) sites of [CH6 N3 ][ZnII (HCOO)3 ]. The doped Co(II) sites in the MOFs perform as SIM with a positive D term of zero-field splitting. The longest magnetic relaxation time is 150 ms (0.2 mol% Co) at 1.8 K under a static field of 0.1 T. Temperature dependency of the relaxation time suggests suppressing magnetic relaxation by reduction of spin-spin interaction upon doping in the rigid framework. Thus, this work represents a proof of concept for the creation of a single-ion doped magnet in the MOF. This simple synthetic strategy will be widely applied for the creation of quantum magnetic materials.

The structure and modified properties of a self-dimerised Cu(II) inclusion complex in γ-cyclodextrins.

Inclusion structures incorporating more than one guest molecule are elusive because confinement alters their molecular properties. We report the solid-state characterization of an inclusion complex comprising two γ-cyclodextrins and two [Cu(2-pyridinemethanolate)(2-pyridinemethanol)]PF6 units. Quantum calculation reveals that interfragment charge transfer occurs. The confined Cu fragment and the unincluded "linear chain [Cu(2-pyridinemethanolate)(2-pyridinemethanol)]PF6" exhibit different properties.

Exploration of glassy state in Prussian blue analogues.

Prussian blue analogues (PBAs) are archetypes of microporous coordination polymers/metal-organic frameworks whose versatile composition allows for diverse functionalities. However, developments in PBAs have centred solely on their crystalline state, and the glassy state of PBAs has not been explored. Here we describe the preparation of the glassy state of PBAs via a mechanically induced crystal-to-glass transformation and explore their properties. The preservation of short-range metal-ligand-metal connectivity is confirmed, enabling the framework-based functionality and semiconductivity in the glass. The transformation also generates unconventional CN- vacancies, followed by the reduction of metal sites. This leads to significant porosity enhancement in recrystallised PBA, enabled by further accessibility of isolated micropores. Finally, mechanical stability under stress for successful vitrification is correlated to defect contents and interstitial water. Our results demonstrate how mechanochemistry provides opportunities to explore glassy states of molecular framework materials in which the stable liquid state is absent.

Simultaneous Spin-Crossover Transition and Conductivity Switching in a Dinuclear Iron(II) Coordination Compound Based on 7,7',8,8'-Tetracyano-p-quinodimethane.

Invited for the cover of this issue are Ryuta Ishikawa and Satoshi Kawata at Fukuoka University and co-workers at Osaka University, Tohoku University, and Kumamoto University, Japan, collaborating within the research project "SOFT CRYSTALS". The image depicts the thermally induced simultaneous switching of magnetism and electrical conductivity in a two-dimensional supramolecular architecture composed of dinuclear FeII spin-crossover complexes and partially charged 7,7',8,8'-tetracyano-p-quinodimethanide radicals. 10.1002/chem.201903934.

Simultaneous Spin-Crossover Transition and Conductivity Switching in a Dinuclear Iron(II) Coordination Compound Based on 7,7',8,8'-Tetracyano-p-quinodimethane.

The reaction of Fe(OAc)2 and Hbpypz with neutral TCNQ results in the formation of [Fe2 (bpypz)2 (TCNQ)2 ](TCNQ)2 (1), in which Hbpypz=3,5-bis(2-pyridyl)pyrazole and TCNQ=7,7',8,8'-tetracyano-p-quinodimethane. Crystal packing of 1 with uncoordinated TCNQ and π-π stacking of bpypz- ligands produces an extended two-dimensional supramolecular coordination assembly. Temperature dependence of the dc magnetic susceptibility and heat capacity measurements indicate that 1 undergoes an abrupt spin crossover (SCO) with thermal spin transition temperatures of 339 and 337 K for the heating and cooling modes, respectively, resulting in a thermal hysteresis of 2 K. Remarkably, the temperature dependence of dc electrical transport exhibits a transition that coincides with thermal SCO, demonstrating the thermally induced magnetic and electrical bistability of 1, strongly correlating magnetism with electrical conductivity. This outstanding feature leads to thermally induced simultaneous switching of magnetism and electrical conductivity and a magnetoresistance effect.

Zero in-Plane Thermal Expansion in Guest-Tunable 2D Coordination Polymers.

Zero in-plane thermal expansion (TE) in a two-dimensional (2D) coordination polymer is demonstrated. The combination of components that expand and those that shrink into zigzag layers results in no net area change in the 2D materials with temperature. Single crystals of [Mn(salen)]2[Mn(N)(CN)4(guest)] (salen = N,N'-ethylenebis(salicylideneaminato), guest = MeOH and MeCN) were prepared, and variable-temperature single-crystal X-ray structural analyses demonstrated that these compounds exhibited both anisotropic positive and negative thermal expansion depending on the guest species. The TE behavior results from distortions of the octahedral coordination geometry of [Mn(salen)]+ units in the zigzag layers. When both guests MeOH and MeCN were incorporated into one material, [Mn(salen)]2[Mn(N)(CN)4(MeOH)0.25(MeCN)0.75], zero in-plane TE resulted in a range of temperature between 380 and 440 K.

Structural transformations of layered structures constructed from Cu(ii)-chloranilate monomer compounds.

Hydrogen-bond supported intercalation compounds constructed from three types of two-dimensional layers and common guests, {(Hha)2[Cu(CA)2(EtOH)2]}n (1), {(Hha)2[Cu(CA)2(EtOH)]}n (2), and {(Hha)2[Cu(CA)2]}n (3) (ha = hexylamine), have been synthesized and characterized. The hexylaminium cations are introduced between the anionic layers of the metal-chloranilate by not only electrostatic interactions but also hydrogen bonding interactions. These compounds show reversible EtOH adsorption and desorption accompanied by a structural transformation. With a change in the interaction between the mononuclear complexes of the host layer, the interaction between the host layer and the intercalated guest cations also changes. Moreover, the mobility and flexibility of the intercalated Hha+ cations enable the rearrangement of the mononuclear complexes while maintaining their layer structure. Thus, these compounds have flexibilities both in the inter- and intra-layers.

Proton conduction via lattice water molecules in oxalato-bridged lanthanide porous coordination polymers.

The proton conducting properties of two different structural types of porous coordination polymers [La2(ox)3(H2O)6]·4H2O (1) and [Er2(ox)3(H2O)6]·12H2O (2), where ox2- = oxalate, were investigated. 1 has a two-dimensional layered structure, whereas 2 has a three-dimensional structure. Both 1 and 2 have hydrophilic one-dimensional channels filled by lattice water molecules with hydrogen-bonding networks. The coordinated H2O molecules are Lewis acidic due to the lanthanoid ions donating protons to lattice-filling H2O molecules, thereby forming efficient proton conduction pathways. Alternating-current impedance analyses of 1 and 2 indicated significant proton conduction (σ = 3.35 × 10-7 S cm-1 at 368 K for 1, 1.79 × 10-6 S cm-1 at 363 K for 2 under RH = 100%, with Ea = 0.35 eV for 1 and 0.47 eV for 2), which was attributed to the Grotthuss mechanism via the lattice H2O molecules.

Bimetallic Cu(I) complex with a pyridine-bridged bis(1,2,3-triazole-5-ylidene) ligand.

A dinuclear copper(i) complex bearing a mesoionic carbene ligand has been prepared from the corresponding silver analogue and its structure determined spectroscopically. The results revealed that two Cu(i) halide salt molecules were bound to the carbon atoms of the pyridine-bridged bis(triazolylidene) moieties rather than the pyridine. Cyclic voltammogram measurements revealed that the two Cu(i) centres underwent a stepwise oxidation, suggesting that both the triazolylidene rings of the ligand could be on the same expanded π-conjugated system. The catalytic hydroboration of styrene derivatives with bis(pinacolato)diborane in the presence of this complex allowed for the ß-selective formation of the corresponding alkylboronate esters.

[Investigation of changes in sexual and ejaculatory functions after holmium laser enucleation of the prostate (HoLEP)].

Changes in sexual function and ejaculatory function in patients who had undergone holmium laser enucleation of the prostate (HoLEP) were investigated using questionnaires. In this study, 77 patients on whom HoLEP was performed at our department from July 2010 to December 2010 were included. Of the 77 patients, the number of patients who could achieve an erection increased from 36 (46.8%) preoperatively to 52 (67.5%) postoperatively after HoLEP. Although postoperative ejaculatory dysfunction was found in 38 (73%) of 52 patients, 47 (90%) experienced orgasms, regardless of ejaculation, which is a high rate. With respect to ejaculatory satisfaction, patients who experienced an ejaculation had significantly higher satisfaction levels than those who did not. These results suggest that changes in postoperative ejaculatory function might affect satisfaction levels of ejaculation.

Slow relaxation of the magnetization of an Mn(III) single ion.

A Mn(III)-salen-type complex with a diamagnetic [Co(III)(CN)6](3-) moiety, [Mn(III)(5-TMAM(R)-salmen)(H2O)Co(III)(CN)6]·7H2O·MeCN [1; 5-TMAM(R)-salmen = (R)-N,N'-(1-methylethylene)bis(5-trimethylammoniomethylsalicylideneiminate], was prepared. From direct-current magnetic susceptibilities, magnetization, and high-field and multifrequency electronic spin resonance measurements on powdered samples, 1 has a significant uniaxial anisotropy. Frequency-dependent alternating-current susceptibility signals were clearly observed, indicating slow magnetic relaxation. Thus, complex 1 behaves as a single-ion magnet.

Mn(III)(tetra-biphenyl-porphyrin)-TCNE single-chain magnet via suppression of the interchain interactions.

A single-chain magnet (SCM) of [Mn(TBPP)(TCNE)]·4m-PhCl(2) (1), where TBPP(2-) = meso-tetra(4-biphenyl)porphyrinate; TCNE(•-) = tetracyanoethenide radical anion; m-PhCl(2) = meta-dichlorobenzene, was prepared via suppression of interchain interactions. 1 has a one-dimensional alternating Mn(III)(porphrin)-TCNE(•-)chain structure similar to those of a family of complexes reported by Miller and co-workers. From a comparison of the static magnetic properties of 1 with other Mn(III)(porphyrin)-TCNE(•-) chains, a magneto-structural correlation between the intrachain magnetic exchange and both the dihedral angle between the mean plane on [Mn(TBPP)(TCNE)] and Mn-N≡C was observed. The ac magnetic susceptibility data of 1 could be fit with the Arrhenius law, indicating that slow magnetic relaxation and ruling out three-dimensional long-range ordering and spin-glass-like behavior. The Cole-Cole plot for 1 was semicircular, verifying that it is an SCM. Therefore, 1 is an ideal single-chain magnet with significantly strong intrachain magnetic exchange interactions beyond the Ising limit.

Photomagnetism of a sym-cis-dithiocyanato iron(II) complex with a tetradentate N,N'-bis(2-pyridylmethyl)1,2-ethanediamine ligand.

A comprehensive study of the magnetic and photomagnetic behaviors of cis-[Fe(picen)(NCS)(2) ] (picen = N,N'-bis(2-pyridylmethyl)1,2-ethanediamine) was carried out. The spin-equilibration was extremely slow in the vicinity of the thermal spin-transition. When the cooling speed was slower than 0.1 K min(-1), this complex was characterized by an abrupt thermal spin-transition at about 70 K. Measurement of the kinetics in the range 60-70 K was performed to approach the quasi-static hysteresis loop. At low temperatures, the metastable HS state was quenched by a rapid freezing process and the critical T(TIESST) temperature, which was associated with the thermally induced excited spin-state-trapping (TIESST) effect, was measured. At 10 K, this complex also exhibited the well-known light-induced excited spin-state-trapping (LIESST) effect and the T(LIESST) temperature was determined. The kinetics of the metastable HS states, which were generated from the freezing effect and from the light-induced excitation, was studied. Single-crystal X-ray diffraction as a function of speed-cooling and light conditions at 30 K revealed the mechanism of the spin-crossover in this complex as well as some direct relationships between its structural properties and its spin state. This spin-crossover (SCO) material represents a fascinating example in which the metastability of the HS state is in close vicinity to the thermal spin-transition region. Moreover, it is a beautiful example of a complex in which the metastable HS states can be generated, and then compared, either by the freezing effect or by the LIESST effect.

Cyano-bridged Mn(III)-M(III) single-chain magnets with M(III)=Co(III), Fe(III), Mn(III), and Cr(III).

A series of isostructural cyano-bridged Mn(III)(h.s.)-M(III)(l.s.) alternating chains, [Mn(III)(5-TMAMsalen)M(III)(CN)(6)]⋅4H(2)O (5-TMAMsalen(2-)=N,N'-ethylenebis(5-trimethylammoniomethylsalicylideneiminate), Mn(III)(h.s.)=high-spin Mn(III), M(III)(l.s.)=low-spin Co(III), Mn-Co; Fe(III), Mn-Fe; Mn(III), Mn-Mn; Cr(III), Mn-Cr) was synthesized by assembling [Mn(III)(5-TMAMsalen)](3+) and [M(III)(CN)(6)](3-). The chains present in the four compounds, which crystallize in the monoclinic space group C2/c, are composed of an [-Mn(III)-NC-M(III)-CN-] repeating motif, for which the -NC-M(III)-CN- motif is provided by the [M(III)(CN)(6)](3-) moiety adopting a trans bridging mode between [Mn(III)(5-TMAMsalen)](3+) cations. The Mn(III) and M(III) ions occupy special crystallographic positions: a C(2) axis and an inversion center, respectively, forming a highly symmetrical chain with only one kind of cyano bridge. The Jahn-Teller axis of the Mn(III)(h.s.) ion is perpendicular to the N(2)O(2) plane formed by the 5-TMAMsalen tetradentate ligand. These Jahn-Teller axes are all perfectly aligned along the unique chain direction without a bending angle, although the chains are corrugated with an Mn-N(axis) -C angle of about 144°. In the crystal structures, the chains are well separated with the nearest inter-chain M⋅⋅⋅M distance being relatively large at 9 Šdue to steric hindrance of the bulky trimethylammoniomethyl groups of the 5-TMAMsalen ligand. The magnetic properties of these compounds have been thoroughly studied. Mn-Fe and Mn-Mn display intra-chain ferromagnetic interactions, whereas Mn-Cr is characterized by an antiferromagnetic exchange that induces a ferrimagnetic spin arrangement along the chain. Detailed analyses of both static and dynamic magnetic properties have demonstrated without ambiguity the single-chain magnet (SCM) behavior of these three systems, whereas Mn-Co is merely paramagnetic with S(Mn)=2 and D/k(B)=-5.3 K (D being a zero-field splitting parameter). At low temperatures, the Mn-M compounds with M=Fe, Mn, and Cr display remarkably large M versus H hysteresis loops for applied magnetic fields along the easy magnetic direction that corresponds to the chain direction. The temperature dependence of the associated relaxation time for this series of compounds systematically exhibits a crossover between two Arrhenius laws corresponding to infinite-chain and finite-chain regimes for the SCM behavior. These isostructural hetero-spin SCMs offer a unique series of alternating [-Mn-NC-M-CN-] chains, enabling physicists to test theoretical SCM models between the Ising and Heisenberg limits.

[Relationship between morcellation efficiency and enucleated tissue weight in holmium laser enucleation of the prostate (HoLEP) for patients with benign prostatic hyperplasia].

OBJECTIVE: We examined the relationship between morcellation efficiency and enucleated tissue weight in holmium laser enucleation of the prostate (HoLEP) for patients with benign prostatic hyperplasia (BPH) retrospectively. METHODS: From January to December 2010, 140 patients with BPH were treated by HoLEP combined with mechanical morcellation with up side down technique by a single surgeon. RESULTS: The mean age was 70.6 years, and the mean enucleated tissue weight was 46.8 g. The mean morcellation time was 9.9 min, and the mean rate of morcellation was 6.7 g/min. No complications were reported relating to morcellation such as bladder injury. Although morcellation time and enucleated tissue weigh were proportionally related (Estimate equation: Y = - 1.186 + 0.813 * X, R^2: 0.814), larger glands with more than 80 g of tissue enucleated did not match this distribution map. Five cases with more than 100 g of enucleated tissue weight required much longer operation time (range 66-90 min) and were disproportioned to tissue weight. Morcellation efficiency tended to decrease when enucleated tissue weight exceeds 80 g and less than average in almost all cases. Morcellation efficiency significantly worsen when enucleated tissue weight exceeds more than 100 g. CONCLUSIONS: Morcellation efficency may decrease in larger gland exceeds 80 g.

Construction of a novel topological frustrated system: a frustrated metal cluster in a helical space.

A novel topologically frustrated pentanuclear cluster helicate [{Cu(II)(µ-L)(3)}(2)Cu(II) (3)(µ(3)-OH)](3+) (L(-)=3,5-bis(2-pyridyl)pyrazolate) has been synthesized and characterized. This cluster has a helical arrangement of ligands around the central metal core. Dzyaloshinsky-Moriya interactions are essential components to observe a gradual magnetization and forbidden transitions of high-field/multi-frequency (HF/MF)-ESR. The origin of the magnetic anisotropy of this compound is influenced by its helical spin structure, and consequently, the Cu(5)-cluster helicate introduces a unique magnetic anisotropy. This observation is a direct evidence of the topological part of the new spin phase in a magnetic system.

[Paclitaxel, ifosfamide, nedaplatin (TIN) for patients with metastatic urothelial cancer].

TIN (ifosfamide 1.5 g/m2 daily for 3 days, paclitaxel 175 mg/m2, and nedaplatin 70 mg/m2 on day 1) was administered to patients with metastatic urothelial cancer previously treated by platinum-based chemotherapy and repeated every 4 weeks. Four patients received maintenance therapy, which consisted of 5'-DFUR 800 mg/day orally for 12 weeks and 1 subsequent course of TIN. This therapy regimen was repeated for 2 years from initiation of TIN. Eleven of 12 patients (91.6%) demonstrated a major response (3 complete responses, 8 partial responses), with durations of response ranging from 3 to 20 months. Progression-free survival time was from 0 to 20 months (median 8 months). One-year progression-free survival rate was 45.8%. Overall survival time was from 2 to 20 months (median 10.5 months). One-year overall survival rate was 53.5%. Grade 3/4 hematologic toxicity involved neutropenia in 100% and thrombocytopenia in 33.3%. Febrile neutropenia was observed in 5 patients (41.6%). Grade 3 nonhematologic toxicity involved malaise in 15.3%. No patient discontinued this therapy because of complications. TIN is a potent, well-tolerated regimen for previously treated patients with urothelial cancer.