Inductive detection of temperature-induced magnetization dynamics of molecular spin systems.

The development and technological applications of molecular spin systems require versatile experimental techniques to characterize and control their static and dynamic magnetic properties. In the latter case, bulk spectroscopic and magnetometric techniques, such as AC magnetometry and pulsed electron paramagnetic resonance, are usually employed, showing high sensitivity, wide dynamic range, and flexibility. They are based on creating a nonequilibrium state either by changing the magnetic field or by applying resonant microwave radiation. Another possible source of perturbation is a laser pulse that rapidly heats the sample. This approach has proven to be one of the most useful techniques for studying the kinetics and mechanism of chemical and biochemical reactions. Inspired by these works, we propose an inductive detection of temperature-induced magnetization dynamics as applied to the study of molecular spin systems and describe the general design and construction of a particular induction probehead, taking into account the constraints imposed by the cryostat and electromagnet. To evaluate the performance, several coordination compounds of VO2+, Co2+, and Dy3+ were investigated using low-energy pulses of a terahertz free electron laser of the Novosibirsk free electron laser facility as a heat source. All measured magnetization dynamics were qualitatively or quantitatively described using a proposed basic theoretical model and compared with the data obtained by alternating current magnetometry. Based on the results of the research, the possible scope of applications of inductive detection and its advantages and disadvantages in comparison with standard methods are discussed.

Lanthanide(III) SMMs with cationic and anionic complex fragments formed by a Schiff base: structure, luminescence, magnetic properties and ab initio calculations.

The syntheses, structures, luminescence and magnetic properties of a new series of Ln(III) complexes of the formula [Ln(L)(H2O)2(DMF)2][Ln(L)2] (in which H2L is N,N'-ethylaminebis[1-phenyl-3-methyl-4-formylimino-2-pyrazoline-5-one]; Ln(III) - Gd (1), Tb (2), or Dy (3) ions). The crystal structures were determined by single-crystal X-ray diffraction measurements for all the above-mentioned complexes. The crystals of these compounds consist of cationic [Ln(L)(H2O)2(DMF)2]+ and anionic [Ln(L)2] moieties which form a 3D supramolecular architecture by the H-bonds and electrostatic forces. Luminescence emission in the visible range was observed for Tb(III) and Dy(III) compounds upon ligand sensitization, with moderate quantum yields of 3.2% for the Dy complex and 24.2% for the Tb analogue. Moreover the Tb(III) complex demonstrates triboluminescence activity. The dynamic magnetization studies revealed that 1 and 2 demonstrate field-induced magnetic relaxation with effective energy barriers, ΔE|kB = 24 K (for 1) and 85 K (for 2), while the Dy complex 3 exhibits slow relaxation of magnetization in zero field with an activation energy of 256 K.

Field induced slow magnetic relaxation in a linear homotrinuclear manganese heterospin coordination compound with S = 7/2 ground state and intriguing spin density distribution.

We report a first example of field-induced (HDC = 2500 Oe) slow magnetization relaxation in the homotrinuclear linear heterospin manganese coordination compound with S = 7/2 ground state, based on the bidentate 3,5-di-tert-butyl-1,2-benzoquinone-1-monooxime (HL) ligand with composition {[MnL3]Mn[MnL3]}.

Ferrocenyl-substituted nitronyl nitroxide in the design of one-dimensional magnets.

By the reaction of M(hfac)2 (M = Mn(II), Co(II), Cu(II), and Zn(II); hfac is the hexafluoroacetylacetonate anion) and ferrocenyl-substituted nitronyl nitroxide (L), we succeeded in the synthesis of stable heterospin complexes: mononuclear [Zn(hfac)2L], trinuclear {[Cu(hfac)2]3L2} and chain polymer [Mn(hfac)2L]n and [Co(hfac)2L]n. The specific steric bulkiness of the ferrocenyl substituent leads to the formation of trans-type coordination polyhedra in the [Mn(hfac)2L]n and [Co(hfac)2L]n chains. The introduction of the ferrocene substituent leads to an effective weakening of intermolecular or interchain magnetic exchange coupling. Ferrimagnetic ordering was observed for one-dimensional complexes [M(hfac)2L]n (M = Mn(II), Co(II)). [Co(hfac)2L]n exhibits features of single-chain magnet behaviour: slow relaxation of magnetization below 13 K is associated with a high coercive field (54 kOe at 2 K).

Effects of solvatomorphism, the nature of a chelating ligand synthon and a counterion on the single crystal XRD structure and SMM properties of paramagnetic monocapped cobalt(II) tris-pyrazoloximates.

A series of monocapped cobalt(II) tris-pyrazoloximates was obtained through the template condensation of the corresponding pyrazoloxime, phenylboronic acid and a suitable cobalt(II) halogenide. Comparing 3-acetylpyrazoloxime versus its methine-containing homolog, the former produced cobalt(II) clathrochelates in substantially higher yields due to the electron donating effect of the methyl substituent, increasing the N-donor ability of its oxime group. Their less N-donor analog with the electron acceptor trifluoromethyl group did not form cobalt(II) complexes of this type. In all their solvent-free and solvent-containing crystals, the encapsulated cobalt(II) ion adopted a high-spin state, as gauged by the Co-N bond lengths of 2.112(4)-2.188(9) Å, and was located almost in the center of its CoN6-coordination polyhedron. Their CoN6-polyhedra had an almost ideal trigonal-prismatic (TP) geometry with distortion angles φ below 4°. This TP-like geometry was assisted by hydrogen bonding between their NH groups and the apical counterion. The absence of methyl groups makes them close to an ideal TP. In contrast, stronger N-H⋯Cl hydrogen bonds occurred in the methyl-containing complex, while the Co-N bond lengths stayed the same at 2.144(2) Å on average. In its solvates with benzene, chloroform and acetone, there is a clear tendency for φ to decrease from 2.7(3)° to 0.47(13)°. The comparable effects of the ribbed methyl substituents, the cross-linking counterion and the lattice solvent on their molecular geometry were observed; the larger the distortions from an ideal TP geometry, the stronger the hydrogen bonds to the corresponding apical halogenide anion. The analysis of the experimental AC- and DC-magnetometry data for their fine-crystalline samples suggests that the passing from the derivative of the methyl-substituted synthon to that of its methine-containing homolog caused a substantial decrease in the magnetic susceptibility value χT and an increase in the QTM contribution to the magnetic relaxation. The effect of a cross-linking halogenide counteranion on the Orbach remagnetization barrier is greater than that of the solvatomorphism of their crystals.

Novel stable ytterbium acetylacetonate-quinaldinate complexes as single-molecule magnets and surprisingly efficient luminophores.

The first Yb complexes comprising a quinoline-2-carboxylate (quinaldinate, Q-) ligand, namely 1D-polymeric [Yb(acac)2(Q)]n (1, acac- is the acetylacetonate (pentane-2,4-dionate) anion) and mononuclear [Yb(acac)2(Q)(Phen)] (2, Phen is 1,10-phenanthroline), are reported. The bifunctionality of both complexes as field-induced single-molecule magnets (SMMs) and near IR luminophores has been revealed. The SMM properties of 1 and 2 have been discussed in terms of the geometry and composition of the coordination environment. Also, 1 is the first example of 1D-polymeric SMMs with the capped octahedral surrounding of Yb3+. The photoluminescence quantum yields (PLQYs) of 1 and 2 are 2 and 4%, respectively. The origins of this difference are discussed. Surprisingly, the PLQY value of 2 is high for compounds comprising a lot of C-H vibrational quenchers, being the highest one for reliably characterized Yb ß-diketonate complexes, and surpassing those for complexes with a broad range of anionic ligands. In this respect, the role of the Phen ligand is to tune the coordination mode of Q- thereby decreasing the energy of coordinating C-O oscillators rather than to act as a typical antenna ligand. These results can give rise to an alternative route to elaborate efficient Yb-based luminophores via the substitution of the ß-diketonate ligands controlled by the introduction of appropriate neutral ligands.

Two Discoveries in One Crystal: σ-Type Oxime Radical as an Unforeseen Building Block in Molecular Magnetics and Its Spatial Structure.

In the present work, the study of the unusual interaction between copper hexafluoroacetylacetonate and the diacetyliminoxyl radical resulted in two discoveries from different fields: the determination of the oxime radical spatial structure and the introduction of an oxime radical into the field of molecular magnetic material design. Oxime radicals are key plausible intermediates in the processes of oxidative CH-functionalization and in the synthesis of functionalized isoxazolines from oximes. Due to the lack of X-ray diffraction data for oxime radicals, the knowledge about their structure is based mainly on indirect approaches, spectroscopic methods (electron paramagnetic resonance and IR), and quantum chemical calculations. The structure of the oxime radical was determined for the first time by stabilizing the diacetyliminoxyl radical in the form of its complex with copper (II) hexafluoroacetylacetonate (Cu(hfac)2), followed by single-crystal X-ray diffraction analysis. Although oxime radicals are known to undergo oxidative coupling with acetylacetonate ligands in transition-metal complexes, a complex is formed with intact hfac ligands. X-ray diffraction studies have shown that the oxime radical is coordinated with copper ions through the oxygen atoms of the carbonyl groups without the direct involvement of the C═N-O• radical moiety. The structure of the coordinated diacetyliminoxyl is in good agreement with the density functional theory (DFT) prediction for free diacetyliminoxyl due to the very weak interaction of the radical molecule with copper ions. Remarkably, both weak ferromagnetic and antiferromagnetic interactions between Cu (II) and oxime radicals have been revealed by modeling the temperature dependence of magnetic susceptibility and confirmed by DFT calculations, rendering diacetyliminoxyl a promising building block for the design of molecular magnets.

Synthesis, X-ray structure and magnetic properties of the apically functionalized monocapped cobalt(II) tris-pyridineoximates possessing SMM behaviour.

The title cobalt(II) pseudoclathrochelate complexes possess an intermediate trigonal prismatic-trigonal antiprismatic geometry. As follows from PPMS data, they exhibit an SMM behaviour with Orbach relaxation barriers of approximately 90 K. Paramagnetic NMR experiments confirmed a persistence of these magnetic characteristics in solution. Therefore, a straightforward apical functionalization of this 3D molecular platform for its targeted delivery to a given biosystem can be performed without substantial changes.

Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica.

The chemical immobilization of cobalt(II) ions in a silica aerogel matrix enabled the synthesis of the first representative example of aerogel-based single-ion magnets. For the synthesis of the lyogels, methyl-trimethoxysilane and N-3-(trimethoxysilyl)propyl ethylenediamine were co-hydrolyzed, then the ethylenediamine groups that were immobilized on the silica matrix enabled the subsequent binding of cobalt(II) ions. Lyogels with various amounts of ethylenediamine moieties (0.1-15 mol %) were soaked in isopropanol solutions of cobalt(II) nitrate and further supercritically dried in carbon dioxide to obtain aerogels with a specific surface area of 210-596 m2·g-1, an apparent density of 0.403-0.740 cm3·g-1 and a porosity of 60-78%. The actual cobalt content in the aerogels was 0.01-1.50 mmol per 1 g of SiO2, which could easily be tuned by the concentration of ethylenediamine moieties in the silica matrix. The introduction of cobalt(II) ions into the ethylenediamine-modified silica aerogel promoted the stability of the diamine moieties at the supercritical drying stage. The molecular prototype of the immobilized cobalt(II) complex, bearing one ethylenediamine ligand [Co(en)(MeCN)(NO3)2], was synthesized and structurally characterized. Using magnetometry in the DC mode, it was shown that cobalt(II)-modified silica aerogels exhibited slow magnetic relaxation in a nonzero field. A decrease in cobalt(II) concentration in aerogels from 1.5 mmol to 0.14 mmol per 1 g of SiO2 resulted in a weakening of inter-ion interactions; the magnetization reversal energy barrier likewise increased from 4 to 18 K.

Series of Fluorinated Benzimidazole-Substituted Nitronyl Nitroxides: Synthesis, Structure, Acidity, Redox Properties, and Magnetostructural Correlations.

A special series of nitronyl nitroxides was synthesized: 2-(benzimidazol-2'-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyls mono-, di-, tri-, or tetrafluorinated on the benzene ring. The structure of all paramagnets was unambiguously confirmed by single-crystal X-ray diffraction. It was found that in crystals, the radicals are assembled into chains due to intermolecular H-bonds between the benzimidazole moiety (H-bond donor) and the nitronyl nitroxide group or benzimidazole ring (H-bond acceptor). The magnetic properties of nitronyl nitroxides depend on the type of binding of radicals by H-bonds. The magnetic motif of 4-fluoro-, 5-fluoro-, 4,6-difluoro-, 4,5,6-trifluoro-, 4,5,7-trifluoro-, and 4,5,6,7-tetrafluoro-derivatives, as well as the nonfluorinated compound, consists of ferromagnetic chains (J/kB ≈ 20-40 K) formed by the McConnell type I mechanism. In the 5,6-difluoro- and 4,5-difluoro-derivatives, the distances between the paramagnetic centers are large, as a result of which the exchange interactions are weak. According to cyclic voltammetry, paramagnets are oxidized reversibly, while their reduction is a quasi-reversible electron transfer (EC mechanism); experimental redox potentials of radicals correlate well with the calculated values. Quantum chemical assessment of the acidity of benzimidazolyl-substituted nitronyl nitroxides revealed that the introduction of fluorine atoms into the benzene ring enhances the acidity of the paramagnets by more than 5 orders of magnitude.

Ni Nanoparticles Stabilized by Hyperbranched Polymer: Does the Architecture of the Polymer Affect the Nanoparticle Characteristics and Their Performance in Catalysis?

Heat-up and hot-injection methods were employed to synthesize Ni nanoparticles (NPs) with narrow size distribution in the presence of hyperbranched pyridylphenylene polymer (PPP) as a stabilizing agent. It was shown that depending on the synthetic method, Ni NPs were formed either in a cross-linked polymer network or stabilized by a soluble hyperbranched polymer. Ni NPs were characterized by a combination of transmission electron microscopy (TEM), scanning TEM, thermogravimetric analysis, powder X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray analysis, and magnetic measurements. The architecture of polymer support was found to significantly effect Ni NPs characteristics and behavior. The Ni NPs demonstrated a high catalytic activity in a model Suzuki-Miyaura cross-coupling reaction. No significant drop in activity was observed upon repeated use after magnetic separation in five consecutive catalytic cycles. We believe that hyperbranched PPP can serve as universal platform for the controllable synthesis of Ni NPs, acting as highly active and stable catalysts.

Magnetically bistable cobalt-dioxolene complexes with a tetradentate N-donor base.

Synthesis and magnetic characterization of a family of cobalt-dioxolene complexes [(Me2TPA)Co(36-DBCat)] (1), [(Me2TPA)Co(36-DBCat)](PF6) (2) and [(Me2TPA)Co(diox-(OMe)3)](BPh4) (3) (Me2TPA = bis(6-methyl-2-pyridyl)methyl-(2-pyridylmethyl)amine; 36-DBCat = dianion of 3,6-di-tert-butylcatechol; diox-(OMe)3 - 2,5-di-tert-butyl-3,3,4-trimethoxy-6-oxocyclohexa-1,4-dienolate) is reported. The neutral complex 1 is found to form hexa- (CoO2N4, 1a) and pentacoordinated (CoO2N3, 1b) isomers. Variable temperature single crystal X-ray diffraction analysis of 1a and 1b clearly indicates the presence of the high-spin divalent metal ion and the dianionic catecholate form of the dioxolene ligand. Oxidation of 1 by ferrocenium hexafluorophosphate results in the formation of the ionic octahedral complex 2, demonstrating thermally induced valence-tautomeric transition (ls-CoIII-36-DBCat ⇄ hs-CoII-36-DBSQ) in the solid state with T1/2 = 175 K (36-DBSQ = radical-anionic semiquinonate form of the redox-ligand). In contrast, aerial oxidation of 1 is accompanied by changes in the structure of dioxolene resulting in oxocyclohexadienolate ligand and the formation of an ionic complex of high-spin divalent cobalt (3). Compounds 1a, 1b, and 3 are found to demonstrate a field-induced single-ion magnet behavior. The analysis of the electronic structures of 1, 2 and 3 with the aid of DFT and SA-CASSCF/NEVPT2 calculations is also given.

Field-Induced Slow Magnetic Relaxation in CoII Cyclopropane-1,1-dicarboxylates.

New CoII substituted malonate field-induced molecular magnets {[Rb6Co3(cpdc)6(H2O)12]∙6H2O}n (1) and [Cs2Co(cpdc)2(H2O)6]n (2) (where cpdc2- stands for cyclopropane-1,1-dicarboxylic acid dianions) were synthesized. Both compounds contain mononuclear bischelate fragments {CoII(cpdc)2(H2O)2}2- where the quasi-octahedral cobalt environment (CoO6) is complemented by water molecules in apical positions. The alkali metal atoms play the role of connectors between the bischelate fragments to form 3D and 2D polymeric structures for 1 and 2, respectively. Analysis of dc magnetic data using the parametric Griffith Hamiltonian for high-spin CoII supported by ab initio calculations revealed that both compounds have an easy axis of magnetic anisotropy. Compounds 1 and 2 exhibit slow magnetic relaxation under an external magnetic field (HDC = 1000 and 1500 Oe, respectively).

Spin transitions in ferric catecholate complexes mediated by outer-sphere counteranions.

A family of ionic ferric catecholate complexes 1-4 bearing a disubstituted 3,6-di-tert-butyl-catecholate ligand (3,6-DBCatH2) and tetradentate tris(2-pyridylmethyl)amine (TPA) was prepared and its spin transitions were investigated. Variation of the outer-sphere counteranions (PF6, BPh4, ClO4, BF4) is accompanied by changes in the magnetic behavior of the compounds under consideration. The crystal structures of complexes 1, 3 and 4 were determined by single crystal X-ray diffraction analysis at 100 K and 293 K. The complexes were characterized by the occurrence of a thermally induced spin-crossover process in the solid state with different degrees of completeness, which was confirmed by the comprehensive spectroscopic investigation (EPR, magnetic susceptibility, Mössbauer, and XAS) of the isolated compounds. Complex 4 containing BF4 anions was found to demonstrate valence tautomeric transition along with spin-crossover. This finding makes compound 4 the first salt-like mononuclear ferric catecholate complex exhibiting valence tautomerism.

Mononuclear Transition Metal Cymantrenecarboxylates as Precursors for Spinel-Type Manganites.

Novel mononuclear cymantrenecarboxylate complexes of transition metals, [Co(H2O)6](CymCO2)2·4H2O (Cym = (η5-C5H4)Mn(CO)3) (1), [Ni(H2O)6](CymCO2)2·4H2O (2), [Zn(H2O)6](CymCO2)2·4H2O (3), [Co(CymCO2)2(imz)2] (imz = imidazole, 4), [Co(CymCO2)2(bpy)2]·2PhMe (bpy = 2,2'-bipyridyl, 5), [Ni(CymCO2)(bpy)2(H2O)][CymCO2]·0.5MePh·2H2O (6), [Cu(CymCO2)2(imz)2] (7), and [Cu(CymCO2)2(bpy)(H2O)] (8), were obtained and characterized by single-crystal X-ray analysis. Complexes 1-3 are isostructural. Magnetism of the Co complexes 1, 4, and 5 was studied; it was shown that they exhibit the properties of field-induced single-molecule magnets with magnetization reversal barriers (ΔE/kB) of 44, 13, and 10 K, respectively. Thermal decomposition of complexes 1-8 was studied by means of DSC and TGA methods. The final products of thermolysis of 1-6 in air, according to powder XRD data, are the pure spinel phases MMn2O4; for the cases of copper complexes, the mixtures of CuMn2O4 and CuO were found in the products.

Change in the Electronic Structure of the Cobalt(II) Ion in a One-Dimensional Polymer with Flexible Linkers Induced by a Structural Phase Transition.

A new 1D-coordination polymer [Co(Piv)2(NH2(CH2)6NH2)]n (1, Piv is Me3CCO2- anion) was obtained, the mononuclear fragments {Co(O2CR)2} within which are linked by µ-bridged molecules of hexamethylenediamine (NH2(CH2)6NH2). For this compound, two different monoclinic C2/c (α-1) and P2/n (ß-1) phases were found at room temperature by single-crystal X-ray diffraction analysis, with a similar structure of chains and their packages in unit cells. The low-temperature phase (γ-1) of crystal 1 at 150 K corresponds to the triclinic space group P-1. As the temperature decreases, the structural phase transition (SPT) in the α-1 and ß-1 crystals is accompanied by an increase in the crystal packing density caused by the rearrangements of both H-bonds and the nearest ligand environment of the cobalt atom ("octahedral CoN2O4 around the metal center at room temperature" → "pseudo-tetrahedral CoN2O2 at 150 K"). The SPT was confirmed by DSC in the temperature range 210-150 K; when heated above 220 K, anomalies in the behavior of the heat flow are observed, which may be associated with the reversibility of SPT; endo effects are observed up to 300 K. The SPT starts below 200 K. At 100 K, a mixture of phases was found in sample 1: 27% α-1 phase, 61% γ-1 phase. In addition, at 100 K, 12% of the new δ-1 phase was detected, which was identified from the diffraction pattern at 260 K upon subsequent heating: the a,b,c-parameters and unit cell volume are close to the structure parameters of γ-1, and the values of the α,ß,γ-angles are significantly different. Further heating leads to a phase transition from δ-1 to α-1, which both coexist at room temperature. According to the DC magnetometry data, during cooling and heating, the χMT(T) curves for 1 form a hysteresis loop with ~110 K, in which the difference in the χMT values reaches 9%. Ab initio calculations of the electronic structure of cobalt(II) in α-1 and γ-1 have been performed. Based on the EPR data at 10 K and the ab initio calculations, the behavior of the χMT(T) curve for 1 was simulated in the temperature range of 2-150 K. It was found that 1 exhibits slow magnetic relaxation in a field of 1000 Oe.

3D-Printed Porous Magnetic Carbon Materials Derived from Metal-Organic Frameworks.

Here we report new porous carbon materials obtained by 3D printing from photopolymer compositions with zinc- and nickel-based metal-organic frameworks, ZIF-8 and Ni-BTC, followed by high-temperature pyrolysis. The pyrolyzed materials that retain the shapes of complex objects contain pores, which were produced by boiling zinc and magnetic nickel particles. The two thus provided functionalities-large specific surface area and ferromagnetism-that pave the way towards creating heterogenous catalysts that can be easily removed from reaction mixtures in industrial catalytic processes.

Tetranuclear Cr-Ln ferrocenecarboxylate complexes with a defect-dicubane structure: synthesis, magnetism, and thermolysis.

Using ferrocenecarboxylic acid (FcCO2H) and triethanolamine (H3tea) as ligands, the isostructural heterotrimetallic complexes [LnIII2CrIII2(OH)2(FcCO2)4(NO3)2(Htea)2]·2MePh·2THF (Ln = Tb (1), Dy (2), Ho (3), Er (4), and Y (5); Fc = (η5-C5H4)(η5-C5H5)Fe; H3tea = N(CH2CH2OH)3) were obtained. In all of the complexes which possess a defective dicubane structure, two doubly deprotonated triethanolamine ligands chelate the chromium ions. However, during the synthesis of 1, an isomeric complex 1a in which Tb3+ is chelated by triethanolamine as a tetradentate ligand, was also isolated as a few single crystals. Magnetic susceptibility measurements revealed dominant antiferromagnetic interactions in the {LnIII2CrIII2} cores of 1-4 leading to the formation of complexes with an uncompensated magnetic moment, while weak Cr-Cr ferromagnetic interactions were detected in the Y analogue. Complexes 1, 2, and 3 exhibit single-molecule magnet properties dominated by an Orbach-type relaxation mechanism with magnetization reversal barriers (Δ/kB) estimated around 54, 75, and 47 K, respectively. The Dy complex exhibits a magnetization hysteresis in an applied magnetic field at temperatures below 4 K. Thermolysis of the complexes was studied by TGA and DSC techniques; the final products obtained under an air atmosphere contain mixed oxide Cr0.75Fe1.25O3 and heterotrimetallic oxide LnCr1-xFexO3 (with x ≈ 0.75) phases.

Two types of Ln2Cu2 hydroxo-trimethylacetate complexes with 0D and 1D motifs: synthetic features, structural differences, and slow magnetic relaxation.

Two series of heterometallic LnIII-CuII compounds containing a butterfly-like tetranuclear metal core were synthesized and characterized by X-ray diffraction and magnetometry. The structures of the new compounds were shown to depend on the nature of the hydroxide used for the synthesis. The reactions of copper(II) and lanthanide(III) salts with Hpiv (Hpiv is trimethylacetic acid) and LiOH in a MeCN-EtOH mixture afford the molecular complexes [Ln2Cu2(µ3-OH)2(piv)8(H2O)4]·4EtOH (1Ln, Ln = Gd, Tb, Dy, Ho, Yb), whereas the similar reactions using NaOH instead of LiOH give the 1D coordination polymers [Na2Ln2Cu2(µ3-OH)2(piv)10(EtOH)2]·EtOH (2Ln, Ln = Gd, Tb, Dy, Ho, Yb). According to ac susceptibility measurements, the DyIII-CuII compounds (1Dy and 2Dy) exhibit slow relaxation of magnetization indicative of single-molecule magnet (SMM) behavior. In the series of YbIII-CuII compounds, only complex 2Yb shows frequency-dependent out-of-phase ac susceptibility signals. This is the first reported example of carboxylate-based YbIII-CuII compound displaying slow magnetic relaxation.

Switchable Aromaticity of Phthalocyanine via Reversible Nucleophilic Aromatic Addition to an Electron-Deficient Phosphorus(V) Complex.

Reversible nucleophilic addition to a phthalocyanine core was observed for the first time for the electron-deficient cationic phosphorus(V) complex [PcP(OMe)2]+, whose reaction with KOH afforded a highly distorted nonaromatic adduct bearing an OH group at one of the α-pyrrolic carbon atoms. This adduct was characterized by single-crystal X-ray diffraction, ESI HRMS, and NMR, and UV-vis spectroscopy, together with quantum-chemical modeling. The acidic treatment of this adduct restored aromaticity and recovered the starting cationic complex. The reversible aromaticity breakage resulted in dramatic changes in the photophysical properties of the studied complex, which could pave the way to novel switchable Pc-based compounds and materials.