A Nanosized {Ni } Cluster with a 'Flying Saucer' Topology Exhibiting Slow Relaxation of Magnetisation Phenomena at Both 15 K and 1.3 K.

A high-nuclearity {Ni} complex (1) with a unique 'flying saucer' motif has been prepared from the organic chelate, α-methyl-2-pyridine-methanol (mpmH), in conjunction with bridging azido (N ) and peroxido (O ) ligands. Magnetic susceptibility measurements revealed the presence of both ferro- and antiferromagnetic exchange interactions between the metal centres in 1, and the stabilization of spin states with appreciable S values at two different temperature regimes. The end-on bridging azido and alkoxido groups are in all likelihood the ferromagnetic mediators, while the η:η:μ-bridging peroxides most likely promote the antiparallel alignment of the metals' spin vectors, yielding an overall non-zero spin ground state for the centrosymmetric compound 1.

Family of Quasi-Isotropic Mn and Mn Complexes Exhibiting Slow Relaxation of the Magnetization.

Slow relaxation of magnetization has been studied for a family of mononuclear Mn complexes and one ferromagnetic dinuclear system, all of them presenting very weak anisotropy. Complexes with formula [{NiL1Mn(HO)(MeOH)}{NiL1}](ClO) (), [Mn{NiL1}](ClO) (), [Mn{NiL2}](ClO) (RR-L2, RR, SS-L2, SS), [Mn{NiL3}](ClO) (RR-L3, RR, SS-L3, SS) and (μ-N)[NiMn(L1)(N)] () are derived from compartmental Schiff bases, in which the Ni environment is square planar and thus diamagnetic. All of the systems have been structurally and magnetically characterized.

Peripheral endocannabinoids in major depressive disorder and alcohol use disorder: a systematic review.

Background: Major Depressive Disorder (MDD) and Alcohol Use Disorder (AUD) are two high-prevalent conditions where the Endocannabinoid system (ECS) is believed to play an important role. The ECS regulates how different neurotransmitters interact in both disorders, which is crucial for controlling emotions and responses to stress and reward stimuli. Measuring peripheral endocannabinoids (eCBs) in human serum and plasma can help overcome the limitations of detecting endocannabinoid levels in the brain.

Magnetocaloric efficiency tuning through solvent-triggered 3D to 2D interconversion in holmium(III)-based dynamic MOFs.

The neutral holmium(III) oxalate octadecahydrate {[Ho(ox)(HO)]·12HO} of mixed hexagonal/decagonal (6·10) 3D net topology shows important changes in the magnetocaloric efficiency upon dehydration/rehydration by heating and water vapor exposition to give the holmium(III) oxalate decahydrate {[Ho(ox)(HO)]·4HO} of hexagonal (6) 2D net topology through the intermediacy of the elusive amorphous anhydrous compound {Ho(ox)}.

Cu(II)-Ln(III) (Ln = Gd, Tb and Dy) complexes of an unsymmetrical NO donor ligand: field induced SMM behaviour of Cu(II)-Tb(III) complexes.

Three new hetero-metallic Cu-Ln complexes [(CuL)Gd(NO)(CHOH)] (1), [(CuL)Tb(NO)(HO)]·[CuL] (2) and [(CuL)Dy(NO)(HO)]·[CuL] (3) have been synthesized using a mono-nuclear Cu(II) complex, [CuL], of an unsymmetrically di-condensed NO donor Schiff base ligand, -(3-methoxysalicylidene)--(salicylidene)-1,2-ethylenediamine (HL). Single crystal X-ray crystallography revealed that complex 1 is a nitrate bridged 1D chain of dinuclear Cu(II)-Gd(III) units whereas in 2 and 3, the dinuclear Cu(II)-Ln(III) units are co-crystallized with a [CuL] unit. The Ln(III) centers are nine coordinated with the geometry of a spherical capped square antiprism for Gd and spherical tricapped trigonal prism for Tb and Dy.

Slow Magnetic Relaxation in Silver(II) Macrocyclic Systems.

The spin-lattice relaxation time has been studied trough alternating-current susceptometry and ultralow-frequency Raman spectroscopy in a family of silver(II)-derived molecular systems with spin / and formulas [Ag(-CTH)(NO)] () and [Ag(-CTH)(ClO)] (), where CTH = -5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. The combination of both techniques demonstrates the occurrence of slow spin magnetic relaxation induced by spin-phonon interaction. The magnetic behavior of these silver(II)-derived systems opens the door to a new cation in the scarce family of = / systems with slow relaxation of magnetization.

Interesting chemical and physical features of the products of the reactions between trivalent lanthanoids and a tetradentate Schiff base derived from cyclohexane-1,2-diamine.

The initial use of a tetradentate Schiff base (LH) derived from the 2 : 1 condensation between 2-hydroxyacetophenone and cyclohexane-1,2-diamine in 4f-metal chemistry is described. The 1 : 2 reaction of Ln(NO)·HO (Ln = lanthanoid or yttrium) and LH in MeOH/CHCl has provided access to isostructural complexes [Ln(NO)(L'H)(MeOH)] in moderate to good yields. Surprisingly, the products contain the corresponding Schiff base ligand L'H possessing six aliphatic -CH- groups instead of the -CH-(CH)-CH- unit of the cyclohexane ring, an unusual ring-opening of the latter has occurred.

Magnetic and optical studies of a new family of multidimensional and multiproperty PO-lanthanide(III) derived systems.

A new family of lanthanide compounds has been synthesized using 1,2-bis(diphenylphosphino)ethane dioxide (dppeO) as an O-donor ligand through the phosphoryl group to lanthanide(III) cations and structurally, magnetically and optically studied. Depending on the lanthanide, two different topologies appear: the two-dimensional structure [Ln(dppeO)(NO)(HO)] (Ln = Ce (1), Sm (2) and Dy (6)) and the one-dimensional structure [Ln(dppeO)(NO)DMF] (Ln = Eu (3), Gd (4) and Tb (5)). Some of the Ln-derived complexes have been used as structural probes, while others have been synthesized to use the specific characteristics of each cation to take advantage of their magnetic/luminescence properties.

Occurrence of slow relaxation of the magnetization in a family of copper(II)/manganese(II) quasi-isotropic complexes with different ground spin states.

A family of copper(II)/manganese(II) new clusters with the formulas [CuNa(L2)(MeOH)(ClO)] (1), [CuII2Mn(,-L3)(MeOH)](ClO) (2SS), [{CuMn(L1)(HO)(MeOH)}{Cu(L1)}](ClO) (3), [(μ-N){CuMn(L2)(HO)}{Cu(L2)](ClO)} (4) and [(μ-N){CuMn(L1)(N)}{CuNa(L1)(MeOH)}](ClO) (5) with L1 = ,'-ethylene-bis(3-methoxysalicylaldiimine), L2 = ,'-ethylene-bis(3-ethoxysalicylaldiimine) and L3 = ,'-cyclohexane-bis(3-ethoxysalicylaldiimine), has been synthesized, and structurally and magnetically characterized. Reduced magnetization studies demonstrate that the magnetic anisotropy of the systems is very small. However, dynamic magnetic studies and ultra-low-frequency Raman spectroscopy confirm the slow relaxation of these systems despite their quasi-isotropic nature, enlarging the range of non-anisotropic slow relaxing molecules.

Novel Co and Ni Metal Complexes and Ferromagnets by the Combination of 2-Pyridyl Oximes with Polycarboxylic Ligands.

The use of 2-pyridyl oximes in metal complexes chemistry has been extensively investigated in the last few decades as a fruitful source of species with interesting magnetic properties. In this work, the initial combination of pyridine-2-amidoxime (pyaoxH) and 2-methyl pyridyl ketoxime (mpkoH) with isonicotinic acid (HINA) and 3,5-pyrazole dicarboxylic acid (Hpdc) has provided access to three new compounds, [Ni(INA)(pyaox)(pyaoxH)(DMF)] (), [Co(mpko)(mpkoH)(OMe)(HO)](ClO) (), and [Co(OH)(Hpdc)(Hpdc)] (). displays a square-planar metal topology, being the first example that bears simultaneously HINA and pyaoxH in their neutral or ionic form.

Slow magnetic relaxation for cobalt(II) complexes in axial bipyramidal environment: an = 1/2 spin case.

A new family of magnetically mononuclear cobalt(II) complexes with formula [{Ni(L)Co(HO)(MeOH)}{Ni(L)}](ClO) where HL1 = bis(,'-bis(3-methoxysalicylidene)ethylene-1,2-diamine) (1), HL2 = bis(,'-bis(3-methoxysalicylidene)propane-1,2-diamine) (2) and [{Cu(L4)}Co](ClO) (3) where HL4 = bis(,'-bis(3-ethoxysalicylidene)cyclohexane-1,2-diamine) have been obtained employing non chiral or enantiomerically pure Schiff bases. The structural studies have been carried out by single crystal X-ray and powder diffraction. Dynamic magnetic studies indicate that some members of this family present field induced slow relaxation of the magnetization and its response has been compared with the magnetically diluted [ZnCo] complex 1D.

Quasi-isotropic SMMs: slow relaxation of the magnetization in polynuclear Cu/Mn complexes.

Three field induced SMMs built from quasi-isotropic cations like Cu and Mn have been characterized, showing that relatively large clusters with quasi-negligible and different ground spin states, = 3/2, 2 or 4, can also exhibit field-induced slow relaxation of magnetization.

Rhodium-catalysed -alkynylation of nitroarenes.

The -alkynylation of nitro-(hetero)arenes takes place in the presence of a Rh(iii) catalyst to deliver a wide variety of alkynylated nitroarenes regioselectively. These interesting products could be further derivatized by selective reduction of the nitro group or palladium-catalysed couplings. Experimental and computational mechanistic studies demonstrate that the reaction proceeds a turnover-limiting electrophilic C-H metalation to the strongly electron-withdrawing nitro group.

Holmium(III) Single-Ion Magnet for Cryomagnetic Refrigeration Based on an MRI Contrast Agent Derivative.

The coexistence of field-induced blockage of the magnetization and significant magnetocaloric effects in the low-temperature region occurs in a mononuclear holmium(III) diethylenetriamine-,,',″,″-pentaacetate complex, whose gadolinium(III) analogue is a commercial MRI contrast agent. Both properties make it a suitable candidate for cryogenic magnetic refrigeration, thus enlarging the variety of applications of this simple class of multifunctional molecular nanomagnets.

Exploring the Role of Intramolecular Interactions in the Suppression of Quantum Tunneling of the Magnetization in a 3d-4f Single-Molecule Magnet.

Hydroxide-bridged FeLn clusters having the general formula [FeLn(μ-OH)(mdea)(SCN)(NO)(HO)]·4HO·2MeCN {Ln = Y (), Dy (), mdea = -methyldiethanolamine} were synthesized and magnetically characterized. The thermal relaxation of the magnetization for and the diluted FeDyY complex (with and without applied field) has been analyzed. The diluted sample shows a dominant QTM at low temperatures that can be removed with a 0.

Single-Ion Anisotropy and Intramolecular Interactions in Ce and Nd Dimers.

This article reports the syntheses, characterization, structural description, together with magnetic and spectroscopic properties of two isostructural molecular magnets based on the chiral ligand ,'-((1,2-diphenyl-(pyridine-2-yl)methylene)-(,/,)-ethane-1,2-diamine), , of general formula [Ln(-)(Cl)]MeOH1.5HO, (Ln = Ce () or Nd ()). Multifrequency electron paramagnetic resonance (EPR), cantilever torque magnetometry (CTM) measurements, and ab initio calculations allowed us to determine single-ion magnetic anisotropy and intramolecular magnetic interactions in both compounds, evidencing a more important role of the anisotropic exchange for the Nd derivative.

Expanding the NUIG MOF family: synthesis and characterization of new MOFs for selective CO adsorption, metal ion removal from aqueous systems, and drug delivery applications.

Metal organic frameworks (MOFs) have attracted considerable attention in recent years due to their use in a wide range of environmental, industrial and biomedical applications. The employment of benzophenone-4,4'-dicarboxylic acid (bphdcH2) in MOF chemistry provided access to the 3D mixed metal MOFs [CoNa2(bphdc)2(DMF)2]n (NUIG2) and [ZnK2(bphdc)2(DMF)2]n (NUIG3), and the 2D homometallic MOF [Co2(OH)(bphdcH)2(DMF)2(H2O)2]n(OH)·DMF (1·DMF). 1·DMF is based on a dinuclear SBU and consists of interpenetrating networks with an sql topology.

Field-induced slow magnetic relaxation and magnetocaloric effects in an oxalato-bridged gadolinium(iii)-based 2D MOF.

The coexistence of field-induced slow magnetic relaxation and moderately large magnetocaloric efficiency in the supra-Kelvin temperature region occurs in the 2D compound [Gd(ox)(HO)]·4nHO (1), a feature that can be exploited in the proof-of-concept design of a new class of slow-relaxing magnetic materials for cryogenic magnetic refrigeration.

Correlating the axial Zero Field Splitting with the slow magnetic relaxation in Gd SIMs.

The field-induced out-of-phase magnetic response of a GdIII complex, selected by its good isolation in the network, has been analyzed and the behaviour of this quasi-isotropic cation has been related to its weak axial zero field splitting ∼0.1 cm-1.

Effective Treatment of Lymphogranuloma venereum Proctitis With Azithromycin.

Background: Lymphogranuloma venereum (LGV) is a sexually transmitted infection caused by Chlamydia trachomatis (CT) serovars L1, L2, and L3 and is endemic among men who have sex with men (MSM) in Europe. We evaluated weekly oral azithromycin 1 g for 3 weeks as a treatment for LGV proctitis.

Methods: This is an open clinical trial with convenience allocation according to treating physician preferences.

Structural and magnetic studies of mononuclear lanthanide complexes derived from N-rich chiral Schiff bases.

A new family of mononuclear lanthanide complexes with the formula [CeIII(L)(NO3)3(MeOH)] (1) and [LnIII(L)(NO3)3]·MeOH where Ln = Gd (2) or Dy (3) and L = N,N'-bis(pyridin-2-ylmethylene)cyclohexane-1,2-diamine has been obtained with the use of enantiomerically pure Schiff bases. Dynamic magnetic studies indicate that 1-3 present field-induced slow relaxation of the magnetization and their response has been compared with the magnetically diluted complexes 2d and 3d. Structural studies have been carried out by single crystal X-ray and powder diffraction.

Family of Isomeric Cu-Ln (Ln = Gd, Tb, and Dy) Complexes Presenting Field-Induced Slow Relaxation of Magnetization Only for the Members Containing Gd.

The strategic design and synthesis of two isomeric Cu complexes, [CuL] and [CuL], of asymmetrically dicondensed NO-donor Schiff-base ligands (where HL and HL are -salicylidene-'-3-methoxysalicylidenepropane-1,2-diamine and -3-methoxysalicylidene-'-salicylidenepropane-1,2-diamine, respectively) have been accomplished via a convenient Cu template method. These two complexes have been used as metalloligands for the synthesis of three pairs of Cu-Ln isomeric complexes [CuL(μ-NO)Ln(NO)(HO)]·CHCN (for complexes -, L = L, and for complexes -, L = L and Ln = Gd, Tb, and Dy, respectively), all of which have been characterized structurally. In all six isomorphous and isostructural complexes, the decacoordinated Ln centers and pentacoordinated Cu centers possess sphenocorona and square-pyramidal geometries, respectively.

Further synthetic investigation of the general lanthanoid(iii) [Ln(iii)]/copper(ii)/pyridine-2,6-dimethanol/carboxylate reaction system: {CuLn} coordination clusters (Ln = Dy, Tb, Ho) and their yttrium(iii) analogue.

In addition to previously studied {CuGd}, {CuGd}, {CuLn} and {CuLn} coordination clusters (Ln = trivalent lanthanide) containing pdm or Hpdm ligands (Hpdm = pyridine-2,6-dimethanol) and ancillary carboxylate groups (RCO), the present work reports the synthesis and study of three new members of a fifth family of such complexes. Compounds [CuLnO(OMe)(NO)(OCCHBu)(pdm)(MeOH)] (Ln = Dy, 1; Ln = Tb, 2; Ln = Ho, 3) were prepared from the reaction of Ln(NO)·xHO (x = 5, 6), CuX·yHO (X = ClO, Cl, NO; y = 6, 2 and 3, respectively), Hpdm, BuCHCOH and EtN (2 : 2.5 : 2 : 1 : 9) in MeCN/MeOH.