Tuning the slow magnetic relaxation with the substituents in anilate bridged bis(dysprosium) complexes.

Dinuclear lanthanide complexes [((HB(pz)3)2Dy)2(µ-Th2An)] (1Dy) and [((HB(pz)3)2Dy)2(µ-ClCNAn)] (2Dy), based on the hydrotris(pyrazol-1-yl)borate (HBpz3-) scorpionate capping ligand and anilate (An2-) bridging linkers, namely homosubstituted dithiophene- and heterosubstituted chlorocyanoanilate, bearing electron-donating and withdrawing substituents at the 3,6-positions of the benzoquinone core, are reported. 1Dy shows an octacoordinated {N6O2} DyIII ion within a D4h distorted square antiprismatic coordination, an ideal geometry for Single-Molecule Magnet (SMM) behavior, given its oblate nature, whereas in 2Dy the octacoordinated DyIII ion adopts a D2d triangular dodecahedron geometry, while maintaining the same {N6O2} coordination sphere. Both complexes show field-induced single molecule magnet (SMM) behaviour, with tuning of the slow magnetic relaxation as a function of the nature of the substituents at the 3,6-positions of the anilate moiety. A comparison of the Arrhenius fitting parameters for 1Dy and 2Dy supports the hypothesis that square antiprismatic DyIII complexes, as 1Dy, exhibit higher energy barriers. This interpretation is supported by ab initio calculations that also shed light on the crucial role of intermolecular dipolar interactions.

Memory effect in ferroelectric polyvinylidene fluoride (PVDF) films via spin crossover probes.

Ferroelectric polymers are of great interest due to their intrinsic processing capabilities, superior to classic inorganic ferroelectric materials. For example, polyvinylidene fluoride (PVDF) and derivatives have been incorporated into multiple device architectures for information storage and transfer. Here we report an additional advantage of organic ferroelectrics as their flexibility allows for the preparation of composites with spin crossover (SCO) probes to tune their ferroelectric parameters by external stimuli. We demonstrate how the saturation polarization and coercive field of a ferroelectric [Fe(NH2trz)3](NO3)2/PVDF composite film depends on the spin state of the [Fe(NH2trz)3](NO3)2, opening a thermal hysteresis and delivering a ferroelectric material with a memory effect. This switching may now be used to tune the function of a device, adding additional information states to the elemental binary logic. Additional evidence of the synergy between the two components of these films was also found in the glass transition of the PVDF component that induces small changes in the paramagnetic component.

Complementary probes for the electrochemical interface.

The functions of electrochemical energy conversion and storage devices rely on the dynamic junction between a solid and a fluid: the electrochemical interface (EI). Many experimental techniques have been developed to probe the EI, but they provide only a partial picture. Building a full mechanistic understanding requires combining multiple probes, either successively or simultaneously. However, such combinations lead to important technical and theoretical challenges. In this Review, we focus on complementary optoelectronic probes and modelling to address the EI across different timescales and spatial scales - including mapping surface reconstruction, reactants and reaction modulators during operation. We discuss how combining these probes can facilitate a predictive design of the EI when closely integrated with theory.

Structure and Electronic Properties of Large Oligomeric Heterometallic 3d/CeIV Polyoxometalates.

Merging the rich chemistry of Ce(IV) polyoxometalates (POMs) with that of 3d polyanions remains a challenge due to the strong competition between these highly oxophilic lanthanide cations and 3d metallic ions for coordination to lacunary molecular metal oxides. We report herein the characterization of an unprecedented water stable hexameric CeIV/CoII POM (Ce12Co6) made of two {(SiW9)2Ce6} units connected to a {(SiW10)2Co6(PO4)2} core. In addition, the pentameric CeIV/NiII compound Ce6Ni8, where two {PW9Ni3W} and a {PW10Ni2} fragments are grafted on a {(PW9)2Ce6} moiety, has been obtained. Magnetic studies of Ce6Ni8 revealed ferromagnetic interactions between the NiII centers constituting the {Ni3PW10} fragments, in agreement with the geometry of such a trinuclear cluster. Related insoluble barium salts of Ce12Co6 and Ce6Ni8 were also prepared, allowing their solid-state electrochemical investigations and showing in particular that in Ce12Co6, both the cobalt, cerium, and silicotungstate moieties are electroactive. Finally, photophysical studies demonstrate the formation of long-lived reduced POMs photosensitized by [Ru(bpy)3]2+, suggesting that Ce12Co6 and Ce6Ni8 could be used as efficient reservoirs of reduction equivalents for photocatalytic reactions.

Terbium and Europium Chlorocyananilate-Based 2D Coordination Polymers.

Two-dimensional layered coordination polymers based on the hetero-substituted 3-chloro-6-cyano-2,5-dihydroxybenzoquinone ligands, hereafter ClCNAn2- anilate, and LnIII ions (Tb and Eu) are reported. Compounds 1 and 2, formulated as Ln2(ClCNAn)3(DMSO)6 (LnIII = Tb, 1; Eu, 2), and their related intermediates 1' and 2', formulated as Ln2(ClCNAn)3(H2O)x·yH2O (x + y likely = 12, Ln = Tb, 1'; and Eu, 2'), were prepared by a conventional one-pot reaction (the latter) and recrystallized from DMSO solvent (the former). Polyhydrated intermediates 1' and 2' show very similar XRPD patterns, while, despite their common stoichiometry, 1 and 2 are not isostructural. Compound 1 consists of a 2D coordination framework of 3,6 topology, where [Tb(DMSO)3]III moieties are bridged by three bis-chelating ClCNAn2- ligands, forming distorted hexagons. Ultrathin nanosheets of 1 were obtained by exfoliation via the liquid-assisted sonication method and characterized by atomic force microscopy, confirming the 2D nature of 1. The crystal structure of 2, still showing the presence of 2D sheets with a "hexagonal" mesh and a common (3,6) connectivity, is based onto flat, non-corrugated slabs. Indeed, at a larger scale, the different "rectangular tiles" show clear roofing in 1, which is totally absent in 2. The magnetic behavior of 1 very likely indicates depopulation of the highest crystal-field levels, as expected for TbIII compounds.

TAMOF-1 as a Versatile and Predictable Chiral Stationary Phase for the Resolution of Racemic Mixtures.

Metal-organic frameworks (MOFs) have become promising materials for multiple applications due to their controlled dimensionality and tunable properties. The incorporation of chirality into their frameworks opens new strategies for chiral separation, a key technology in the pharmaceutical industry as each enantiomer of a racemic drug must be isolated. Here, we describe the use of a combination of computational modeling and experiments to demonstrate that high-performance liquid chromatography (HPLC) columns packed with TAMOF-1 as the chiral stationary phase are efficient, versatile, robust, and reusable with a wide array of mobile phases (polar and non-polar). As proof of concept, in this article, we report the resolution with TAMOF-1 HPLC columns of nine racemic mixtures with different molecular sizes, geometries, and functional groups. Initial in silico studies allowed us to predict plausible separations in chiral compounds from different families, including terpenes, calcium channel blockers, or P-stereogenic compounds. The experimental data confirmed the validity of the models and the robust performance of TAMOF-1 columns. The added value of in silico screening is an unprecedented achievement in chiral chromatography.

Manipulating Intermetallic Charge Transfer for Switchable External Stimulus-Enhanced Water Oxidation Electrocatalysis.

Electrocatalytic processes involving the oxygen evolution reaction (OER) present a kinetic bottleneck due to the existence of linear-scaling relationships, which bind the energies of the different intermediates in the mechanism limiting optimization. Here, we offer a way to break these scaling relationships and enhance the electrocatalytic activity of a Co-Fe Prussian blue modified electrode in OER by applying external stimuli. Improvements of ≈11 % and ≈57 % were achieved under magnetic field (0.2 T) and light irradiation (100 mW cm-2 ), respectively, when working at fixed overpotential, η=0.6 V at pH 7. The observed enhancements strongly tie in with the intermetallic charge transfer (IMCT) intensity between Fe and Co sites. Density Functional Theory simulations suggest that tuning the IMCT can lead to a change of the OER mechanism to an external stimuli-sensitive spin crossover-based pathway, which opens the way for switchable electrocatalytic devices.

Synthesis and characterization of highly diluted polyanionic iron(II) spin crossover systems.

Spin crossover (SCO) complexes, through their reversible spin transition under external stimuli, can work as switchable memory materials. Here, we present a protocol for the synthesis and characterization of a specific polyanionic iron SCO complex and its diluted systems. We describe steps for its synthesis and the determination of crystallographic structure of the SCO complex in diluted systems. We then detail a range of spectroscopic and magnetic techniques employed to monitor the spin state of the SCO complex in both diluted solid- and liquid-state systems. For complete details on the use and execution of this protocol, please refer to Galán-Mascaros et al.1.

A quantum spin liquid candidate isolated in a two-dimensional CoIIRhIII bimetallic oxalate network.

A quantum spin liquid (QSL) is an elusive state of matter characterized by the absence of long-range magnetic order, even at zero temperature, and by the presence of exotic quasiparticle excitations. In spite of their relevance for quantum communication, topological quantum computation and the understanding of strongly correlated systems, like high-temperature superconductors, the unequivocal experimental identification of materials behaving as QSLs remains challenging. Here, we present a novel 2D heterometallic oxalate complex formed by high-spin Co(ii) ions alternating with diamagnetic Rh(iii) in a honeycomb lattice. This complex meets the key requirements to become a QSL: a spin ½ ground state for Co(ii), determined by spin-orbit coupling and crystal field, a magnetically-frustrated triangular lattice due to the presence of antiferromagnetic correlations, strongly suppressed direct exchange interactions and the presence of equivalent interfering superexchange paths between Co centres. A combination of electronic paramagnetic resonance, specific heat and ac magnetic susceptibility measurements in a wide range of frequencies and temperatures shows the presence of strong antiferromagnetic correlations concomitant with no signs of magnetic ordering down to 15 mK. These results show that bimetallic oxalates are appealing QSL candidates as well as versatile systems to chemically fine tune key aspects of a QSL, like magnetic frustration and superexchange path geometries.