Effect of coordinated anions on ferromagnetically coupled Dy2 zero-field single-molecule magnets.

A new hydrazone Schiff base ligand was condensed from 2-hydroxy-3-methoxybenzaldehyde and pyrimidine-4-carbohydrazide {H2L = (E)-N'-(2-hydroxy-3-methoxybenzylidene)pyrimidine-4-carbohydrazide}, which was used to assemble two new Dy2 complexes Dy2L2(DMF)2(NO3)2 (1) and Dy2L2(DMF)2(AcO)2 (2). Notably, the coordinated anions have a subtle effect on the coordination configurations of the Dy3+ ions and the magnetic properties of the two Dy2 complexes. The Dy3+ ions in 1 and 2 have the same N2O5 coordination environment but show the triangular dodecahedron and the biaugmented trigonal prism coordination configurations, respectively. Magnetic measurements revealed that both 1 and 2 have intramolecular ferromagnetic interactions between the Dy3+ ions and show single-molecule magnet behaviors at 0 Oe, with Ueff/k values of 58.2 K for 1 and 59.9 K for 2. These magnetic properties may be explained by theoretical calculations.

Magnetodielectric Effect in a Triangular Dysprosium Single-Molecule Toroics.

Single-molecule toroics are molecular magnets with vortex distribution of magnetic moments. The coupling between magnetic and electric properties such as the magnetodielectric effect will provide potential applications for them. Herein, the observation of significant magnetodielectric effect in a triangular Dy3 crystal with toroidal magnetic moment and multiple magnetic relaxations is reported. The analysis of magnetic and electric properties implies that the magnetodielectric effect is closely related to the strong spin-lattice coupling, magnetic interactions of Dy3+ ions, as well as molecular packing models.

The influence of light on the field-induced magnetization dynamics of two Er(III) coordination polymers with different halogen substituents.

Photocontrolled magnetic properties are fundamental for the applications of molecular magnets, which have the features of high time and space resolution; however, such magnetic properties are highly challenging to be achieved owing to the weak light-matter interactions. Herein, the influence of in situ light irradiation on the field-induced magnetization dynamics of two Er(III) coordination polymers 1 and 2 with the same coordination skeletons but different halogen substituents was studied. 1 and 2, and their in situ photoexcited products 1a and 2a, display field-induced magnetization dynamics based on Orbach and/or Raman processes. The magnetization dynamics are fine-modulated by the synergetic effect of light irradiation and a ligand substituent, due to the charge re-distribution of the excited states of the ligand.

Reversible single-crystal to single-crystal transformation between triangular single-molecule toroics.

We report a method for synthesizing single-molecule magnets through a single-crystal to single-crystal transformation. This process yields two single-molecule magnets with similar triangular Dy3 cores but distinct solvents and space groups achieved via solvent exchange. Magnetic properties reveal that both Dy3 molecules exhibit similar toroidal moments but manifest diverse multiple magnetization dynamic behaviors owing to the spin-lattice coupling influence from different solvent molecules.

Protein Containing the GGDEF Domain Affects Motility and Biofilm Formation in Vibrio cholerae and is Negatively Regulated by Fur and HapR.

Objective: This study aimed to investigate whether the VCA0560 gene acts as an active diguanylate cyclase (DGC) in Vibrio cholerae and how its transcription is regulated by Fur and HapR. Methods: The roles of VCA0560 was investigated by utilizing various phenotypic assays, including colony morphological characterization, crystal violet staining, Cyclic di-GMP (c-di-GMP) quantification, and swimming motility assay. The regulation of the VCA0560 gene by Fur and HapR was analyzed by luminescence assay, electrophoretic mobility shift assay, and DNase I footprinting. Results: VCA0560 gene mutation did not affect biofilm formation, motility, and c-di-GMP synthesis in V. cholerae, and its overexpression remarkably enhanced biofilm formation and intracellular c-di-GMP level but reduced motility capacity. The transcription of the VCA0560 gene was directly repressed by Fur and the master quorum sensing regulator HapR. Conclusion: Overexpressed VCA0560 functions as an active DGC in V. cholerae, and its transcription is repressed by Fur and HapR.

Promoted Photocatalytic Hydrogen Evolution by Tuning the Electronic State of Copper Sites in Metal-Organic Supramolecular Assemblies.

The electronic state in terms of charge and spin of metal sites is fundamental to govern the catalytic activity of a photocatalyst. Herein, we show that modulation of the electronic states of Cu sites, without changing the coordination environments, of two metal-organic supramolecular assemblies based on π⋅⋅⋅π stacking can significantly improve photocatalytic activity. The use of these heterogeneous photocatalysts, without using noble metal cocatalysts, resulted in an increase of the hydrogen production rate from 522 to 3620 µmol h-1 g-1 . A systematical analysis revealed that the charge density and spin density of the metal centers are efficiently modulated via the modulation of the coordination fields around active copper (II) centers by the variation of the non-coordination groups of terminal ligands, leading to the significant enhancement of photocatalytic activity. This work provides an insight into the electronic state of active metal centers for designing high-performance photocatalysts.

Ferromagnetically coupled single-chain magnets exhibiting a magnetic hysteresis of 0.42 Tesla in cyano-bridged FeIII2MII (M = Ni, Fe) coordination polymers.

The synthesis, single-crystal structures and magnetic properties of two new double-zigzag-chain cyano-bridged heterobimetallic {[MII(Py-NOH)2][FeIII(Tp*)(CN)3]2}·H2O ([FeIII2MII]) (Py-NOH = 4-pyridinealdoxime, Tp* = tris(3,5-dimethylpyrazol-1-yl)borohydride, M = Ni (1), Fe (2)) compounds are reported. The crystal structures of both compounds were determined by single-crystal X-ray diffraction. Complexes 1 and 2 are isostructural, with the crystal structure comprising neutral double-zigzag (4,2-ribbon-like) bimetallic chains. The FeIII ion is coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp* anions. However, the MII ion is surrounded by four cyanide nitrogen atoms and two nitrogen atoms from two Py-NOH ligands. The crystal structures and magnetic studies demonstrate that both complexes behave as single-chain magnetics (SCMs) with intrachain ferromagnetic coupling. Furthermore, [FeIII2NiII] exhibits an excellent coercive field of 0.42 T at 1.8 K, among cyano-bridged 3d transition-metal-based SCMs reported thus far. Preliminary theoretical calculations provide a deep understanding of the magnetic properties of [FeIII2NiII].

Alkyl Chains Modulated Magnetization Dynamics of Mononuclear Trigonal Prismatic CoII Complexes.

Four benzeneboron-capped mononuclear CoII complexes with different alkyl substitutions on the fourth position of phenylboronic acid were obtained. The CoII ions are all wrapped by the pocket-like ligands and located in trigonal prismatic coordination geometries. Alternating-current magnetic susceptibility measurements reveal that they show different magnetization dynamics, such as distinct relaxation rates at the same temperature, the faster QTM rates for the ethyl and propyl substituted complexes, as well as different relaxation processes. Magneto-structural correlation study reveals that the various deviations of coordination geometry of CoII ion, diverse crystal packings and possible different vibration modes of substituents caused by modifying alkyl chains are the key factors affecting the magnetization dynamics. This work demonstrates that the alkyl chains even locating far away from the metal center can have a large impact on the magnetic behavior of the CoII complex with a very rigid coordination geometry, offering a new perspective towards transition metal based single-molecule magnets.

Boosting the mono-axial crystal field in stable high-coordinate Dy(III) single-ion magnets by substitution of the phenoxy axial ligand.

Synthesis of air-stable and high-performance single-molecule magnets (SMMs) is challenging. Here, a heptadentate pentapyridyldiamine (BPA-TPA) ligand and fine-tuned axial phenoxy ligands are used to synthesize two triangular dodecahedral Dy(III) complexes [Dy(BPA-TPA)(4-methoxy-PhO)](BPh4)2·3CH2Cl2 (4) and [Dy(BPA-TPA)(2,4-dimethyl-PhO)](BPh4)2·0.85CH2Cl2 (5). Both complexes have high effective barriers exceeding 400 K and magnetic hysteresis up to 8 K, which is ascribed to one strong and short Dy-O bond combined with seven weak Dy-N bonds. Ab initio calculations reveal the thermally activated quantum tunneling of magnetization through the first excited Kramers doublet, due to the presence of a strong axial Dy-O crystal ligand. Substitution of the phenoxy ligand leads to more constrained vibrations, improving the magnetic hysteresis behavior for 5.

Regulating Magnetic Relaxations of Cyano-Bridged {DyIII MoV } Systems by Tuning the N-Sites in ß-Diketone Ligands.

Cyano-bridged 4d-4f molecular nanomagnets have re-called increasing research interests in molecular magnetism since they offer more possibilities in achieving novel nanomagnets with versatile structures and magnetic interactions. In this work, four ß-diketone ligands bearing different substitution N-sites were designed and synthesized, namely 1-(2-pyridyl)-3-(3-pyridyl)-1,3-propanedione (HL1 ), 1,3-Bis (3-pyridyl)-1,3-propanedione (HL2 ), 1-(4-pyridyl)-3-(3-pyridyl)-1,3-propanedione (HL3 ), and 1,3-Bis (4-pyridyl)-1,3-propanedione (HL4 ), to tune the magnetic relaxation behaviors of cyano-bridged {DyIII MoV } systems. By reacting with DyCl3 ⋅ 6H2 O and K4 Mo(CN)8 ⋅ 2H2 O, four cyano-bridged complexes, namely {[Dy[MoV (CN)8 ](HL1 )2 (H2 O)3 ]} ⋅ 6H2 O (1), {[Dy[MoV (CN)8 ](HL2 )(H2 O)3 (CH3 OH)]}2 ⋅ 2CH3 OH ⋅ 3H2 O (2), {[Dy[MoV (CN)8 ](HL3 )(H2 O)2 (CH3 OH)] ⋅ H2 O}n (3), and {[Dy[MoV (CN)8 ](HL4 )2 (H2 O)3 ]} ⋅ 2H2 O⋅CH3 OH (4) were obtained. Structural analyses revealed that 1 and 4 are binuclear complexes, 2 has a tetragonal structure, and 3 exhibits a stair-like polymer chain structure. The DyIII ions in all complexes have eight-coordinated configurations with the coordination spheres DyO7 N1 for 1 and 4, DyO6 N2 for 2, and DyO5 N3 for 3. Magnetic measurements indicate that 1 is a zero-field single-molecule magnet (SMM) and complexes 2-4 are field-induced SMMs, with complex 4 featuring a two-step relaxation process. The magnetic characterizations and ab initio calculations revealed that changing the N-sites in the ß-diketone ligands can effectively alter the structures and magnetic properties of cyano-bridged 4d-4f nanomagnets by adjusting the coordination environments of the DyIII centers.

Synergy of Magnetic Anisotropy and Ferromagnetic Interaction Triggering a Dimeric Cr(II) Zero-Field Single-Molecule Magnet.

A novel CrII-dimeric complex, [CrIIN(SiiPr3)2(µ-Cl)(THF)]2 (1), has been successfully constructed using a bulky silyl-amide ligand. Single-crystal structure analysis reveals that complex 1 exhibits a binuclear motif, with a Cr2Cl2 rhombus core, where two equivalent tetra-coordinate CrII centers in the centrosymmetric unit display quasi-square planar geometry. The crystal structure has been well simulated and explored by density functional theory calculations. The axial zero-field splitting parameter (D < 0) with a small rhombic (E) value is unambiguously determined by systematic investigations of magnetic measurements, high-frequency electron paramagnetic resonance spectroscopy, and ab initio calculations. Remarkably, ac magnetic susceptibility data unveil that 1 features slow dynamic magnetic relaxation typical of single-molecule magnet behavior with Ueff = 22 K in the absence of a dc field. This increases up to 35 K under a corresponding static field. Moreover, magnetic studies and theoretical calculations point out that a non-negligible ferromagnetic coupling (FMC) exists in the dimeric Cr-Cr units of 1. The coexistence of magnetic anisotropy and FMC contributes to the first case of CrII-based single-molecule magnets (SMMs) under zero dc field.

Understanding the Magnetic Relaxation Mechanism in Mixed-Valence Dilanthanide Complexes with Metal-Metal Bonding: A Theoretical Investigation.

Theoretical investigations on mixed-valence dilanthanide complexes (CpiPr5)2Ln2I3 (Ln = Tb, Dy, and Ho) indicate that the total spin of the 4f shell couples preferentially to the σ electron spin and then to the orbital angular momentum, improving the strength of spin-orbit coupling (SOC) for each magnetic center. On the other hand, the concentration of negative charges containing the delocalized σ electron in the axial direction leads to a large crystal-field (CF) splitting. Both strong SOC and large CF splitting lead to the largest energy barrier Ueff of such complexes up to now. In addition, our calculations show that the introduction of σ electron can better suppress the quantum tunneling of magnetization in the ground spin-orbit state, and the Ueff of (CpiPr5)2Ln2I3 is expected to originate from the contribution of both Ln ions under such strong Ln-σ exchange coupling.

Ligand Modulation of the Structures and Magnetic Relaxation in Triangular Dy3 Complexes Based on a Tricompartmental Scaffold.

Using a novel tricompartmental hydrazone ligand, a set of trinuclear Dy3 complexes has been isolated and structurally characterized. Complexes Dy3 ⋅ Cl, Dy3 ⋅ Br, and Dy3 ⋅ ClO4 feature a similar overall topology but different anions (Cl- , Br- , or ClO4 - ) in combination with exogenous OH- and solvent co-ligands, which is found to translate into very different magnetic properties. Complex Dy3 ⋅ Cl shows a double relaxation process with fast quantum tunneling of the magnetization, probably related to the structural disorder of µ2 -OH- and µ2 -Cl- co-ligands. Relaxation of the magnetization is slowed down for Dy3 ⋅ Br and Dy3 ⋅ ClO4 , which do not show any structural disorder. In particular, fast quantum tunneling is suppressed in case of Dy3 ⋅ ClO4 , resulting in an energy barrier of 341 K and magnetic hysteresis up to 3.5 K; this makes Dy3 ⋅ ClO4 one of the most robust air-stable trinuclear SMMs. Magneto-structural relationships of the three complexes are analyzed and rationalized with the help of CASSCF/RASSI-SO calculations.

A synergistic therapeutic nano-eyedrop for dry eye disease based on ascorbic acid-coupled exosomes.

Dry eye disease (DED), a complex ocular surface disease with a high prevalence rate, is associated with corneal injury, excess oxidative stress and inflammation. Current therapeutic strategies, including artificial tears and anti-inflammatory agents, are unable to address all the deleterious factors or to achieve a clinical cure due to their temporary or side effects. Here, we prepared a multiple-functional eyedrop based on the deposition of gold nanoparticles (AuNPs) reduced by ascorbic acid (AA) onto the exosomal phospholipid membrane of mesenchymal stem cell (mExo)-derived exosomes in situ (mExo@AA). The therapeutic value of mExo@AA for DED was demonstrated in a mouse DED model. Combining the benefits of mExo and AA, mExo@AA effectively improves corneal epithelium recovery and anti-inflammation capacity, decreases corneal reactive oxygen species, and restores tear secretion without adverse effects. Thus, this study suggests that mExo@AA is effective and safe as a therapeutic agent for the treatment of DED.

X-Ray Triggered Coordination-Bond Breakage in Dysprosium-Organic Framework and its Impact on Magnetic Properties.

Photosensitive lanthanide-based single-molecule magnets (Ln-SMM) are very attractive for their potential applications in information storage, switching, and sensors. However, the light-driven structural transformation in Ln-SMMs hardly changes the coordination number of the lanthanide ion. Herein, for the first time it is reported that X-ray (λ=0.71073 Å) irradiation can break the coordination bond of Dy-OH2 in the three-dimensional (3D) metal-organic framework Dy2 (amp2 H2 )3 (H2 O)6 ⋅ 4H2 O (MDAF-5), in which the {Dy2 (OPO)2 } dimers are cross-linked by dianthracene-phosphonate ligands. The structural transformation proceeds in a single-crystal-to-single-crystal (SC-SC) fashion, forming the new phase Dy2 (amp2 H2 )3 (H2 O)4 ⋅ 4H2 O (MDAF-5-X). The phase transition is accompanied by a significant change in magnetic properties due to the alteration in coordination geometry of the DyIII ion from a distorted pentagonal bipyramid in MDAF-5 to a distorted octahedron in MDAF-5-X.

Photocontrollable Magnetism and Photoluminescence in a Binuclear Dysprosium Anthracene Complex.

By incorporating photoreactive anthracene moieties into binuclear Dy2O2 motifs, we obtain two new compounds with the formulas [Dy2(SCN)4(L)2(dmpma)4] (1) and [Dy2(SCN)4(L)2(dmpma)2(CH3CN)2] (2), where HL is 4-methyl-2,6-dimethoxyphenol and dmpma is dimethylphosphonomethylanthracene. Compound 1 contains face-to-face π-π interacted anthracene groups that meet the Schmidt rule for a [4 + 4] photocycloaddition reaction, while stacking of the anthracene groups in compound 2 does not meet the Schmidt rule. Compound 1 undergoes a reversible single-crystal-to-single-crystal structural transformation upon UV-light irradiation and thermal annealing, forming a one-dimensional coordination polymer of [Dy2(SCN)4(L)2(dmpma)2(dmpma2)]n (1UV). The process is concomitant with changes in the magnetic dynamics and photoluminescent properties. The spin-reversal energy barrier is significantly increased from 1 (55.9 K) to 1UV (116 K), and the emission color is changed from bright yellow for 1 to weak blue for 1UV. This is the first binuclear lanthanide complex that exhibits synergistic photocontrollable magnetic dynamics and photoluminescence. Ab initio calculations are conducted to understand the magnetostructural relationships of compounds 1, 1UV, and 2.

Five-Coordinated Dysprosium Single-Molecule Magnet Functionalized by the SMe Group.

A five-coordinate mononuclear Dy(III) complex with a C4v geometry (square-pyramid), [Dy(X)(DBP)2(TMG(H))2] [X = 3-(methylthio)-1-propoxide, DBP = 2,6-di-tert-butylphenoxide, and TMG(H) = 1,1,3,3-tetramethylguanidine] (1), was designed and synthesized. The complex displays a large anisotropy barrier of 432 cm-1 in the absence of a dc magnetic field benefiting from the strong interaction between the phenolate and Dy(III) ion. Ab initio calculations reveal that the most possible relaxation pathway is going through the second excited state. The terminal SMe group in the apical position furnishes the possibility of depositing it on the Au surface by the strong Au-S bond.

Pseudo-mono-axial ligand fields that support high energy barriers in triangular dodecahedral Dy(iii) single-ion magnets.

The synthesis of air-stable, high-performance single-molecule magnets (SMMs) is of great significance for their practical applications. Indeed, Ln complexes with high coordination numbers are satisfactorily air stable. However, such geometries easily produce spherical ligand fields that minimize magnetic anisotropy. Herein, we report the preparation of three air-stable eight-coordinate mononuclear Dy(iii) complexes with triangular dodecahedral geometries, namely, [Dy(BPA-TPA)Cl](BPh4)2 (1) and [Dy(BPA-TPA)(X)](BPh4)2·nCH2Cl2 (X = CH3O- and n = 1 for 2; L = PhO- and n = 2 for 3), using a novel design concept in which the bulky heptadentate [2,6-bis[bis(2-pyridylmethyl)amino]methyl]-pyridine (BPA-TPA) ligand enwraps the Dy(iii) ion through weak coordinate bonds leaving only a small vacancy for a negatively charged (Cl-), methoxy (CH3O-) or phenoxy (PhO-) moiety to occupy. Magnetic measurements reveal that the single-molecule magnet (SMM) property of complex 1 is actually poor, as there is almost no energy barrier. However, complexes 2 and 3 exhibit fascinating SMM behavior with high energy barriers (U eff = 686 K for 2; 469 K for 3) and magnetic hysteresis temperatures up to 8 K, which is attributed to the pseudolinear ligand field generated by one strong, highly electrostatic Dy-O bond. Ab initio calculations were used to show the apparent difference in the magnetic dynamics of the three complexes, confirming that the pseudo-mono-axial ligand field has an important effect on high-performance SMMs compared with the local symmetry. This study not only presents the highest energy barrier for a triangular dodecahedral SMM but also highlights the enormous potential of the pseudolinear Dy-L ligand field for constructing promising SMMs.

H-NS Represses Biofilm Formation and c-di-GMP Synthesis in Vibrio parahaemolyticus.

Objective: This study aimed to investigate the regulation of histone-like nucleoid structuring protein (H-NS) on biofilm formation and cyclic diguanylate (c-di-GMP) synthesis in Vibrio parahaemolyticus RIMD2210633. Methods: Regulatory mechanisms were analyzed by the combined utilization of crystal violet staining, quantification of c-di-GMP, quantitative real-time polymerase chain reaction, LacZ fusion, and electrophoretic-mobility shift assay. Results: The deletion of hns enhanced the biofilm formation and intracellular c-di-GMP levels in V. parahaemolyticus RIMD2210633. H-NS can bind the upstream promoter-proximal DNA regions of scrA, scrG, VP0117, VPA0198, VPA1176, VP0699, and VP2979 to repress their transcription. These genes encode a group of proteins with GGDEF and/or EAL domains associated with c-di-GMP metabolism. Conclusion: One of the mechanisms by which H-NS represses the biofilm formation by V. parahaemolyticus RIMD2210633 may be via repression of the production of intracellular c-di-GMP.