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Model calculations indicate that the increasement of Ueff becomes tiny when N–Dy–N angle is large. Thus, the construction of near-linear two-coordinate dysprosium(III) SMMs with high Ueff and TB using bulky imidazolin-2-iminato ligands is feasible.

The current study evaluated the efficacy and safety of a denosumab biosimilar, QL1206 (60 mg), compared to placebo in postmenopausal Chinese women with osteoporosis and high fracture risk. At 31 study centers in China, a total of 455 postmenopausal women with osteoporosis and high fracture risk were randomly assigned to receive QL1206 (60 mg subcutaneously every 6 months) or placebo. From baseline to the 12-month follow-up, the participants who received QL1206 showed significantly increased bone mineral density (BMD) values (mean difference and 95% CI) in the lumbar spine: 4.780% (3.880%, 5.681%), total hip :3.930% (3.136%, 4.725%), femoral neck 2.733% (1.877%, 3.589%) and trochanter: 4.058% (2.791%, 5.325%) compared with the participants who received the placebo. In addition, QL1206 injection significantly decreased the serum levels of C-terminal crosslinked telopeptides of type 1 collagen (CTX): -77.352% (-87.080%, -66.844%), and N-terminal procollagen of type l collagen (P1NP): -50.867% (-57.184%, -45.217%) compared with the placebo over the period from baseline to 12 months. No new or unexpected adverse events were observed. We concluded that compared with placebo, QL1206 effectively increased the BMD of the lumbar spine, total hip, femoral neck and trochanter in postmenopausal Chinese women with osteoporosis and rapidly decreased bone turnover markers. This study demonstrated that QL1206 has beneficial effects on postmenopausal Chinese women with osteoporosis and high fracture risk.

The synthesis of fluoride-bridged 1Dy, 2Dy and hepta-nuclear 3Dy dysprosium complexes is reported here and a hydroxy-bridged dinuclear dysprosium complex 4Dy is synthesized for comparison.

This is the first time that circularly polarized luminescence and obvious magneto-optical effects have been observed simultaneously in a single-molecule magnet.

Photodynamic therapy (PDT) is a non-invasive method for cancer treatment that relies on the generation of excess reactive oxygen species (ROS), upon excitation of photosensitizer (PS), to eradicate tumor cells. However, the overexpress of endogenous antioxidants in tumor cells will eliminate the ROS and restrict the therapeutic efficacy of PDT. Herein, a novel type of PS was developed by conjugating cinnamaldehyde (CA), a kind of oxidative stress amplified agent, with porpholactam through a hydrazone bond. The new PS retains the photophysical properties of porpholactam, which displays high singlet oxygen quantum yield for the PDT function. The results of in vitro experiments performed including ROS assay and the cytotoxicity in cancer cells suggest that the rational design of the novel porpholactam-CA derivatives result in enhanced ROS generation upon irradiation, providing a possible approach to achieve enhanced therapeutic effects in PDT.

By the bridging action of the 6-chloro-2-hydroxypyridine (Hchp) ligand and the terminal coordination role of the homochiral ligand, (-)/(+)-3-trifluoroacetyl camphor (l-Htfc/d-Htfc), a pair of enantiomerically pure dysprosium(III) dinuclear complexes, [Dy2(l-tfc)4(chp)2(MeOH)2] (l-1) and [Dy2(d-tfc)4(chp)2(MeOH)2] (d-1), was obtained. Their circular dichroism (CD) spectra verified their enantiomeric nature. Magnetic investigation indicated that they exhibit ferromagnetic interaction and good zero field single-molecule magnet (SMM) properties. The Ueff/k values of l-1 and d-1 at 0 Oe are 180.5 and 181.3 K, respectively, which are large values for homochiral Dy(III) SMMs. A reasonable explanation for the magnetic properties of l-1 and d-1 was supplied by ab initio calculations. Remarkably, magnetic circular dichroism (MCD) investigation revealed that the chiral Dy2 enantiomers show a strong magneto-optical Faraday effect at room temperature, suggesting potential applications in magneto-optical devices.

Multiferroic materials have attracted great interest because of their underlying new science and promising applications in data storage and mutual control devices. However, they are still very rare and highly imperative to be developed. Here, we report an organic–inorganic hybrid perovskite trimethylchloromethylammonium chromium chloride (TMCM–CrCl3), showing the coexistence of magnetic and electric orderings. It displays a paraelectric–ferroelectric phase transition at 397 K with an Aizu notation of 6/mFm, and spin-canted antiferromagnetic ordering with a Néel temperature of 4.8 K. The ferroelectricity originates from the orientational ordering of TMCM cations, and the magnetism is from the [CrCl3]− framework. Remarkably, TMCM–CrCl3 is the first experimentally confirmed divalent Cr2+-based multiferroic material as far as we know. A new category of hybrid multiferroic materials is pointed out in this work, and more Cr2+-based multiferroic materials will be expectedly developed in the future., An organic–inorganic hybrid perovskite Trimethylchloromethylammonium chromium(ii) chloride (TMCM–CrCl3) can simultaneously show excellent ferroelectricity and antiferromagnetism, which is the first experimentally confirmed Cr2+-based multiferroic material.

The study of lanthanide (Ln)-transition-metal (TM) heterometallic clusters which play key roles in various high-tech applications is a rapid growing field of research. Despite the achievement of numerous Ln-TM cluster compounds comprising one Ln atom, the synthesis of Ln-TM clusters containing multiple Ln atoms remains challenging. Here, we present the preparation and self-assembly of a series of Au-bridged heterometallic clusters containing multiple cerium (Ce) atoms via on-surface coordination. By employing different pyridine and nitrile ligands, the ordered coordination assemblies of clusters containing 2, 3 and 4 Ce atoms bridged by Au adatoms are achieved on Au(111) and Au(100), as revealed by scanning tunneling microscopy. Density functional theory calculations uncover the indispensable role of the bridging Au adatoms in constructing the multi-Ce-containing clusters by connecting the Ce atoms via unsupported Ce-Au bonds. These findings demonstrate on-surface coordination as an efficient strategy for preparation and organization of the multi-Ln-containing heterometallic clusters., The preparation of lanthanide-transition metal clusters containing multiple lanthanide atoms remains challenging. Here, the authors present the controlled on-surface formation of ligand-stabilized heterometallic Ce/Au clusters containing two, three and four Ce atoms bridged by Au adatoms.

Mechanochromic luminescent materials have attracted considerable attention because of their interesting color switching behavior under mechanical grinding or hydrostatic pressure. Here, the intrigu...

A pair of structurally-similar and stable 8-coordinate high-spin Fe(ii) and Fe(iii) compounds have been obtained. Both compounds exhibit field-induced slow magnetic relaxation behaviour. The Fe(iii) compound represents the first example of 8-coordinate Fe(iii) single-molecule magnets (SMM).

Homoleptic tris(6,6′-dimethyl-2,2′-bipyridine) rare earth metal complexes M(κ2-dmbp)3 (M = Y, Tb, Dy, Ho, Er; dmbp = 6,6′-dimethyl-2,2′-bipyridine) were synthesized by in situ reduction of 3 equiv. of dmbp with excess KC8 in the presence of 1 equiv. of rare earth metal trihalides. All compounds were characterized by X-ray crystallography, UV-Vis-NIR spectroscopy, infrared (IR) spectroscopy, elemental analysis, and magnetic measurements. While the structural parameters and spectroscopic data confirmed the existence of the trivalent rare earth metal cation and three dmbp radical anions, the electron paramagnetic resonance (EPR) spectrum and the measured magnetic moment of Y(κ2-dmbp)3 indicated that two parallel dmbp radical anions were antiferromagnetically coupled. For paramagnetic rare earth metal ions, room temperature magnetic susceptibility values indicated a weak ferromagnetic interaction between the metal ion and the remaining dmbp radical. Density functional theory (DFT) calculations were performed on Y(κ2-dmbp)3 to gain insight into the electronic structures of these homoleptic metal complexes. The computational results were consistent with the structural, spectroscopic, and magnetic data for a S = 1/2 ground state and spin densities mostly residing on one dmbp radical anion, while the spins on the other two parallel dmbp radical anions being antiferromagnetically coupled.

A series of mononuclear lanthanide complexes with the formula [Hex4N][Ln(DBM)4] (1Ln) (Ln = Nd and Tb), [But4N][Dy(DBM)4] (2), [Et4N][Dy(DBM)4] (3), [PhCH2N(CH3)3][Dy(DBM)4] (4) and [Hex4N][Dy(TTA)4] (5) formed by four β-diketonate ligands (i.e. DBM = dibenzoylmethane, TTA = 2-thenoyltrifluoroacetone) and four organic counter ammonium cations (i.e. Hex4N = tetrahexylammonium, But4N = tetrabutylammonium, Et4N = tetraethylammonium and PhCH2N+(CH3)3) were structurally and magnetically characterized. The organic ammonium as contactless cation pairs with [Ln(β-diketonate)4]−1 moieties, the impact of different remote organic cations and the first coordination sphere comprising distinct β-diketonates on their SMM performance were elaborately studied. This is an efficient method by virtue of the interaction of the remote organic ion pair to modulate their single-molecule magnetic (SMM) properties. More importantly, the tetrakis β-diketonate Dy(III) anion can be almost intactly grafted on functional GaN substrate through an anion exchange reaction, resulting in diminishing slow magnetic relaxation behavior, which presents potential application in future SMM devices.

The first-row transition metal compounds, [MII(L1)2](ClO4)2 (M = Ni (1); Co (2)), have been prepared by treatment of a neutral tetradentate ligand (L1 = N2,N9-dibutyl-1,10-phenanthroline-2,9-dicarboxamide) with metal perchlorate salts in MeOH. Both compounds have been structurally characterized by X-ray crystallography and it was found that the coordination numbers are 6 and 7, respectively. The reaction of 6,6′-bis(2-tbutyl-tetrazol-5-yl)-2,2′-bipyridine (L2) with hydrated FeII(ClO4)2 afforded a 8-coordinate Fe(II) compound, [FeII(L2)2](ClO4)2 (3); however its reaction with hydrated CoII(ClO4)2 resulted in 6-coordinate [CoII(L2)2](ClO4)2. It is interesting to observe field-induced slow magnetic relaxation in the 7-coordinate Co(II) compound 2 and 8-coordinate Fe(II) compound 3, which further supports the validity of designing high coordination number compounds as single-molecule magnets. Direct current magnetic studies demonstrate that 2 has a very large positive D value (56.2 cm−1) and a small E value (0.66 cm−1), indicating easy plane magnetic anisotropy. Consistent with the larger D value, an effective spin-reversal barrier of Ueff = 100 K (71.4 cm−1) is obtained, which is the highest value reported for 7-coordinate Co(II) complexes with a pentagonal bipyramidal geometry. In contrast, 8-coordinate Fe(II) compound 3 exhibits uniaxial magnetic anisotropy.

Molecular magnets are molecular-based magnetic materials that can exhibit slow magnetic relaxation behaviors similar to macroscopic magnets on a single-molecule scale, and have potential applications in ultrahigh-density information storage. Studying the electronic structure and magnetic coupling properties of molecular magnets through appropriate theoretical models and calculation methods is an effective method to analyze the magnetic-structural relationship which is significant for guiding experimental design. In this review, the analysis of molecular magnetism by density functional theory combined with broken-symmetry (DFT-BS), effective Hamiltonian and ab initio method is introduced through representative examples in our group.

Symmetry and axiality are thought to be guides toward the pursuit of high energy barrier and blocking temperature for the dysprosium (III) (DyIII) single-molecule magnets (SMMs). The DyIII complexe...

We investigate a family of dinuclear dysprosium metallocene single-molecule magnets (SMMs) bridged by methyl and halogen groups [Cp'2 Dy(μ-X)]2 (Cp'=cyclopentadienyltrimethylsilane anion; 1: X=CH3- ; 2: X=Cl- ; 3: X=Br- ; 4: X=I- ). For the first time, the magnetic easy axes of dysprosium metallocene SMMs are experimentally determined, confirming that the orientation of them are perpendicular to the equatorial plane which is made up of dysprosium and bridging atoms. The orientation of the magnetic easy axis for 1 deviates from the normal direction (by 10.3°) due to the stronger equatorial interactions between DyIII and methyl groups. Moreover, its magnetic axes show a temperature-dependent shifting, which is caused by the competition between exchange interactions and Zeeman interactions. Studies of fluorescence and specific heat as well as ab initio calculations reveal the significant influences of the bridging ligands on their low-lying exchange-based energy levels and, consequently, low-temperature magnetic properties.

Oxidative stress is one of the hallmarks of ischemic stroke. Catalase-based (CAT) biomimetic complexes are emerging as promising therapeutic candidates that are expected to act as neuroprotectants for ischemic stroke by decreasing the damaging effects from H2O2. Unfortunately, these molecules result in the unwanted production of the harmful hydroxyl radical, HO•. Here, we report a series of salen-based tri-manganese (Mn(III)) metallocryptands (1-3) that function as catalase biomimetics. These cage-like molecules contain a unique "active site" with three Mn centers in close proximity, an arrangement designed to facilitate metal cooperativity for the effective dismutation of H2O2 with minimal HO• production. In fact, significantly greater oxygen production is seen for 1-3 as compared to the monomeric Mn(Salen) complex, 1c. The most promising system, 1, was studied in further detail and found to confer a greater therapeutic benefit both in vitro and in vivo than the monomeric control system, 1c, as evident from inter alia studies involving a rat model of ischemic stroke damage and supporting histological analyses. We thus believe that metallocryptand 1 and its analogues represent a new and seemingly promising strategy for treating oxidative stress related disorders.

Photodynamic therapy (PDT) is a non-invasive treatment modality against a range of cancers and nonmalignant diseases, however one must be aware of the risk of causing phototoxic reactions after treatment. We herein report a bioinspired design of next-generation photosensitizers (PSs) that not only effectively produce ROS but undergo fast metabolism after treatment to overcome undesirable side effects. We constructed a series of β-pyrrolic ring-opening seco-chlorins, termed beidaphyrin (BP), beidapholactone (BPL), and their zinc(II) derivatives (ZnBP and ZnBPL), featuring intense near-infrared absorption and effective O

Investigating the magnetic anisotropy and magnetic interactions of lanthanide complexes is of vital importance for an in-depth understanding of their magnetic properties. Herein, we reported the synthetic, structural and magnetic studies of a triangular type dysprosium complex (1Dy3, [{(Cp)(Tp*)Ln(μ-bta)}3·2(thf)], Cp = C5H5, Tp* = hydrotris(3,5-dimethyl-1-pyrazolyl)borate anion, btaH = 1H-1,2,3-benzotriazole). 2Dy ([(Cp)Dy(Tp)2·C7H8], Tp = hydrotris(1-pyrazolyl)borate) was investigated by single-crystal angular-resolved susceptibility measurements and computational studies to help understand the magnetic anisotropy of 1Dy3. The easy axis of three DyIII ions in 1Dy3 was orientated out of the triangular dysprosium plane. The exchange interactions were small (−0.85 cm−1) but caused remarkable effects on magnetic relaxations at low temperature. In the temperature range from 2 K to 4 K, magnetic relaxation occurred via the exchange-coupled low-lying excited states, inhibiting magnetic hysteresis. Our study showed that weak intramolecular magnetic interactions can significantly affect the dynamic properties in the low temperature regime.

We report here porphodilactol derivatives and their corresponding metal complexes. These systems show promise as “all-in-one” phototheranostics and are predicated on a design strategy that involves controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. The requisite balance was achieved by tuning the aromaticity of these porphyrinoid derivatives and forming complexes with one of two lanthanide cations, namely Gd3+ and Lu3+. The net result led to a metalloporphodilactol system, Gd-trans-2, with seemingly optimal ISC efficiency, photothermal conversion efficiency and fluorescence properties, as well as good chemical stability. Encapsulation of Gd-trans-2 within mesoporous silica nanoparticles (MSN) allowed its evaluation for tumour diagnosis and therapy. It was found to be effective as an “all-in-one” phototheranostic that allowed for NIR fluorescence/photoacoustic dual-modal imaging while providing an excellent combined PTT/PDT therapeutic efficacy in vitro and in vivo in 4T1-tumour-bearing mice., We report here porphodilactol derivatives and their corresponding metal complexes as “all-in-one” phototheranostics by controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation.

Enhancing the exchange interaction between magnetic ions is a long-term target in molecular magnetism. Endohedral metallofullerenes (EMFs) provide a possibility for achieving such a goal by imprisoning multiple magnetic centers inside the confined inner space of a fullerene cage. Here, we report a new member of dimetallic azafullerene Dy2@C79N via crystallographic determination for the first time. Magnetic studies indicate that the strong ferromagnetic coupling between lanthanide ions and unpaired electrons enables Dy2@C79N to be a favorable SMM with large energy barrier of U = 669 K and observable hysteresis loops below 24 K.

Compared with homopolymers, the copolymers exhibit improved properties, providing a broad application prospect. Herein, we report the visible-light-induced living/controlled radical copolymerizatio...

OBJECTIVE To assess the efficacy of tranexamic acid (TXA) in reducing total blood loss and transfusion, and the risk of thromboembolic events in patients undergoing periacetabular osteotomy (PAO) and high tibial osteotomy (HTO). METHODS A systematic literature search was performed using PubMed, the Cochrane Central Register of Controlled Trials (CENTRAL), Embase (Ovid), Medline (Ovid), and Web of Science. ClinicalTrials.gov, American Academy of Orthopaedic Surgeons (AAOS), and Orthopaedic Trauma Association (OTA) conference proceedings were also searched to gain more eligible studies. The primary outcome measure was total blood loss and the blood transfusion rate of the TXA group versus control. The meta-analysis was conducted using the RevMan 5.3 and Stata 14.0 software. RESULTS A total of six studies were included involving 665 patients. Three studies were PAO, and the other three were HTO. The total blood loss in PAO (WMD, -330.49; 95% CI, -390.16 to -270.83; P

Three new iso-structural ammonium metal formates of [dmpnH2 ][M2 (HCOO)6 ], in which dmpnH2 2+ =N,N'-dimethyl-1,3-propylenediammoium and M=divalent Co, Zn and Mg ions, are reported. They possess niccolite metal formate frameworks with long-shaped cavities for the accommodation of dmpnH2 2+ cations. The three materials display reversible phase transitions of similar mechanism from ordered, antipolar or antiferroelectric, low-temperature phases in space group C2/c, to disordered, paraelectric, high-temperature phases in space group P 3 ‾ 1c, with quite high critical temperatures of 366, 370, and 334 K for Co, Zn, and Mg members, respectively. On warming, the dmpnH2 2+ cation experiences an ordered state with gradual increase of the local vibration motions of the central CH2 and terminal CH3 groups, a partially disordered state with gradually enhanced flipping motion between the major and minor orientations, and finally a twisting or rotating motion after the phase transition, accompanied by prominent anisotropic thermal expansions and dielectric anomalies/relaxations. The phase transition characters and relevant properties also exhibit a subtle metal-dependence. The Co member shows spin-canted antiferromagnetism below the Neel temperature of 16.1 K, with unusual large spontaneous magnetization and coercive field.

Magneto-luminescent molecules have significant applications in data storage and quantum computing. However, design of these bi-functional molecules coupled with magnetic behavior and photoluminescence is still challenging. In this work, we report a metallofullerene DyErScN@Ih-C80 exhibiting single-molecule magnet (SMM) behavior and near-infrared emission. For DyErScN@Ih-C80, two functional lanthanide metal ions of Dy3+ (SMM function) and Er3+ (luminescent function) are integrated inside a fullerene cage using a trimetallic nitride template, and its structure has been unambiguously characterized by single-crystal X-ray diffraction. Magnetic measurements revealed that DyErScN@Ih-C80 behaves as a SMM with a blocking temperature up to 9 K resulting from the intramolecular magnetic interaction between Dy3+ and Er3+ ions. Moreover, DyErScN@Ih-C80 exhibits temperature-dependent near-infrared emission around 1.5 μm with multiple splitting peaks from Er3+, which arises from the influence of Dy3+ ion. This study provides a new strategy to synthesize new magneto-luminescent molecule materials.

By the bridging action of the 6-chloro-2-hydroxypyridine (Hchp) ligand and the terminal coordination role of the homochiral ligand, (-)/(+)-3-trifluoroacetyl camphor (l-Htfc/d-Htfc), a pair of enantiomerically pure dysprosium(III) dinuclear complexes, [Dy

Charge transfer (CT) and electron transfer (ET) underlie the various applications of viologen compounds. However, the CT and ET in solids are still insufficiently understood and difficult to control, which is challenging but fundamental to the design of multifunctional materials. Our strategy is to attempt a delicate control of CT and ET by subjecting model compounds to pressure. In this work, a series of viologens of the same cation with different anions show anion-dependent color and piezo-/photochromism due to ground-state CT and stimuli-induced ET; the ease of solid-state ET can be tuned in the order of Cl- > Br- > I-/BF4-/PF6-/ClO4-. With in situ high pressure UV-vis experiments, we also observed unexpectedly the pressure-induced solid-state ET in [H2bcpV]·I2 besides the pressure modulation of the CT absorption. It proves pressure is a more powerful stimulus than light in tuning solid-state CT and ET.

Although many emerging new phenomena have been unraveled in two dimensional (2D) materials with long-range spin orderings, the usually low critical temperature in van der Waals (vdW) magnetic material has thus far hindered the related practical applications. Here, we show that ferromagnetism can hold above 300 K in a metallic phase of 1T-CrTe2 down to the ultra-thin limit. It thus makes CrTe2 so far the only known exfoliated ultra-thin vdW magnets with intrinsic long-range magnetic ordering above room temperature. An in-plane room-temperature negative anisotropic magnetoresistance (AMR) was obtained in ultra-thin CrTe2 devices, with a sign change in the AMR at lower temperature, with −0.6% and +5% at 300 and 10 K, respectively. Our findings provide insights into magnetism in ultra-thin CrTe2, expanding the vdW crystals toolbox for future room-temperature spintronic applications.

Enhancing the exchange interaction between magnetic ions is a long-term target in molecular magnetism. Endohedral metallofullerenes (EMFs) provide a possibility for achieving such a goal by imprisoning multiple magnetic centers inside the confined inner space of a fullerene cage. Here, we report a new member of dimetallic azafullerene Dy2@C79N via crystallographic determination for the first time. Magnetic studies indicate that the strong ferromagnetic coupling between lanthanide ions and unpaired electrons enables Dy2@C79N to be a favorable SMM with large energy barrier of U = 669 K and observable hysteresis loops below 24 K.

Two dysprosium complexes bearing unsupported Dy–Ge/Sn metal–metal bonds are reported here, wherein the Dy–Ge and Dy–Sn bonds both contain relatively large covalency. The complexes exhibit slow relaxation of magnetization at zero field with energy barriers of 485 and 620 K, respectively, and the blocking temperature of 6 K.