Change In Spin State Research Articles

Switching the Multiple Function Channels in 2D Hofmann-Type Coordination Polymers.

The modulation of multifunctional molecular materials by utilizing the stimuli-responsive spin crossover (SCO) has attracted considerable research interest due to its potential applications in information storage and smart switching devices. However, the complexity of achieving the integration and interconnection of multiple functions constitutes a formidable challenge. Herein, we present a pair of 2D FeII-based Hofmann-type coordination polymers (HTCPs), namely {FeII(aep)2[AgI(CN)2]2}·0.3DMF (1) and {FeII(avp)2[AgI(CN)2]2} (2), using fluorescence ligands 4-[2-(9-anthracenyl)ethynyl]pyridine (aep) and 4-[2-(9-anthryl)vinyl]pyridine (avp), respectively. Both complexes exhibit one-step SCO, with transition temperatures of 216 K for complex 1 and 255 K for complex 2. Their dielectric properties align well with the observed magnetic behaviors, demonstrating the dielectric transition process caused by the change of spin state. A variable-temperature fluorescence study reveals the coexistence of SCO and luminescent properties in both complexes, with a remarkable synergistic coupling observed in complex 2 due to the shorter distance between the SCO centers and the fluorophore. These findings underscore the potential of HTCPs as a promising platform for modulating multiple functions. By manipulating their spin states through external stimuli, SCO materials will promisingly advance the development of next-generation molecule-based sensors and devices.

Proton-Induced Switching of Paramagnetism: Reversible Conversion between a Low and High Spin CoIII Center within a Heterobimetallic Core.

The development of molecular species with switchable magnetic properties has been a long-standing challenge in chemistry. One approach involves binding an analyte, such as protons, to a compound to trigger a change in magnetism. Transition metal complexes have been targeted for this type of magnetic modulation because they can undergo changes in their spin states. However, heterobimetallic complexes have had limited utility because of a lack of ligands that create differentiated structures around each metal center that are often necessary to regulate the electronic and magnetic properties. To circumvent this problem, we have used a tripodal ligand with phosphinic amido groups to prepare a complex with a discrete [CoIII(μ-OH)FeIII] core and an overall system spin of ST = 5/2. Deprotonation readily produces a species with a unique [CoIII(μ-O)FeIII] core and an ST = 1/2 system spin. X-ray diffraction studies, electron paramagnetic resonance spectroscopy, and Mössbauer spectroscopy pinpoint the hexacoordinate CoIII center as the cause of this spin change: the typical SCo = 0 spin state of the CoIII center in the [CoIII(μ-OH)FeIII] complex switches to a rare SCo = 2 spin state in the [CoIII(μ-O)FeIII] analogue; this change turns on antiferromagnetic coupling between the two metal centers. Computational studies link an increase in π bonding within the Co-oxido unit to the change in the CoIII spin state. The conversion is reversible and provides a blueprint for using oxido/hydroxido ligands within a heterobimetallic core to regulate the spin state of a metal site and thus modulate the paramagnetism of a system.

Multistate Transition Metal Carbonyl Bonding Beyond Minimum Energy Pathway: Nonlocality of Spin-Orbit Interaction.

Transition metal carbonyl and transition metal dinitrogen are fundamental chemical complexes in many important biological and catalytic processes. Interestingly, binding between a transition metal (TM) atom and carbonyl or dinitrogen results in spin state change. However, no study has evaluated the spin-orbit (SO) effect along the association pathway of any TM-CO or TM-N2 bond. Using multireference calculations with SO interaction, we calculated the association potential energy curve for 11 electronic states for the spin crossover reactions: Ni + CO → NiCO and Ni + N2 → NiN2. Through this multistate calculation, we found that the commonly used minimum energy pathway (MEP) gives reasonable energies for the asymptotes but has an incorrect physical picture in the intermediate bond length. MEP assumes strong SO at the energy crossing point that allows for direct spin crossover from the triplet to singlet state, but multireference calculations showed that SO interactions strengthen at bond length regions, 2.3-2.5 Å before the crossing point. Furthermore, this results in a spin barrier of 0.15 eV along the Ni adsorbate association pathway. These calculations provide a new understanding of the overlooked yet important effect of the spin barrier on the association process, which can change the association rate by several orders of magnitude.

Spin-state switching of indium-phthalocyanine on Pb(100).

Indium(iii) phthalocyanine chloride deposited on Pb(100) is studied by scanning tunnelling spectroscopy at cryogenic temperatures. The Cl ions are dissociated and the remaining indium phthalocyanine (InPc) is observed in two states with the metal ion pointing to (↓) or away (↑) from the substrate. Isolated molecules and islands with a superstructure and a unit cell of four inequivalent molecules, namely one InPc↑ and three InPc↓ in different sites, are observed. Using atomic resolution images of the substrate the adsorption sites and azimuthal orientation of InPc are determined and a structure model is proposed. Conductance spectra of the lowest unoccupied molecular orbital reveal differences that depend on the adsorption sites and azimuthal orientations of the complexes. Only InPc↑ molecules exhibit Shiba states, indicating the presence of a localized spin. By electron extraction isolated complexes as well as molecules in islands are converted from InPc↑ to InPc↓. At the same time, their spin state changes, as indicated by the disappearance of the Shiba states.

Nutation-orbit resonances: The origin of the chaotic rotation of Hyperion and the barrel instability

While numerous planetary and asteroid satellites show evidence for non-trivial rotation states, none are as emblematic as Hyperion, which has long been held as the most striking example of chaotic spin-orbit evolution in the Solar System. Nevertheless, an analytically tractable theory of the full 3D spin-orbit dynamics of Hyperion has not been developed. We derive the Hamiltonian for a spinning axisymmetric satellite in the gravitational potential of a planet without assuming planar or principal axis rotation and without averaging over the spin period. Using this model, we demonstrate the emergence of resonances between the nutation and orbital frequencies that act as the primary drivers of the spin dynamics. This analysis reveals that, contrary to long-held belief, Hyperion is not tumbling chaotically. Instead, it lies near or in a nutation-orbit resonance that is first-order in eccentricity, allowing it to rotate quasi-regularly. The most reliable observations are consistent with either nonchaotic motion or chaos that is orders of magnitude smaller than originally claimed. A separate phenomenon, the so-called barrel instability, is shown to be related to a different set of nutation-orbit resonances that generalize the planar spin-orbit resonances. Finally, we show that changes in spin states over long timescales are best understood by considering chaotic diffusion of quasi-conserved quantities.

Exploring Charge Redistribution at the Cu/Co6Se8 Interface.

This study investigates the electronic interactions and charge redistribution at the dopant-support interface using a Cu/Co6Se8 cluster construct. Specifically, the redox cluster series [Cu3Co6Se8L6]n ([1-Cu3]n; n = 0, -1, -2, -3; L = Ph2PNTol-, Ph = phenyl, Tol = p-tolyl) spanning four distinct oxidation states is synthesized and characterized using a multitude of techniques, including multinuclear NMR, UV-vis, XANES, and X-ray crystallography. Structural investigations indicate that the clusters are isostructural and chiral, adopting a pseudo-D3 symmetry. Paramagnetic 31P NMR spectroscopy and solution-phase magnetic measurements together with DFT calculations are employed to interrogate the electronic structure and spin-state changes across the [1-Cu3]3- to 1-Cu3 redox series, revealing that the copper edge sites retain a +1 oxidation state while the Co/Se core becomes increasingly oxidized, yielding a highly zwitterionic cluster.

Chemically Separable Co(II) Spin-State Isomers.

The phenomenon of spin crossover involves coordination complexes with switchable spin states. This spin state change is accompanied by significant geometric changes such that low and high spin forms of a complex are distinct isomers that exist in equilibrium with one another. Typically, spin-state isomers interconvert rapidly and are similar enough in polarity to prevent their independent separation and isolation. We report here the first example, to our knowledge, of cobalt(II) spin-state isomers that can be physically separated. The reaction of Mo2(dpa)4 (dpa = 2,2'-dipyridylamide) with CoBr2 produces a mixture of two heterometallic compounds with a linear, metal-metal-bonded Mo[Formula: see text]Mo-Co chain. The complexes, SC-[BrMo2(dpa)4Co]Br (SC-2) and HS-[BrMo2(dpa)4CoBr] (HS-2), have identical compositions (Mo2Co(dpa)4Br2) but different ground spin states and coordination geometries of the Co(II) ion. In the solid state, SC-2 undergoes incomplete spin crossover from an S = 1/2 state to an S = 3/2 state, and HS-2 has a high spin, S = 3/2, ground state, as confirmed by SQUID magnetometry and EPR spectroscopy. Crystallographic analyses of SC-2 and HS-2 show that SC-2 has an elongated Co-Br distance relative to HS-2 and is best described as the salt [BrMo2(dpa)4Co]Br. This limits SC-2's solubility in nonpolar solvents and allows for the physical separation of the two isomers. Solution studies of SC-2 and HS-2 indicate that SC-2 and HS-2 interconvert slowly relative to the NMR time scale. Additional solution-state EPR and UV-vis absorption measurements demonstrate that the choice of solvent polarity determines the predominant isomer present in solution.

Mononuclear high-spin iron(III) phthalocyanines

2,9(or 10),16(or 17), 23(or 24)-Tetradecyloxycarbonylphthalocyaninatoiron, FeTDPc, and 2,3,9,10,16,17,23,24-octadecyloxycarbonylphthalocyaninatoiron, FeODPc, were synthesized and characterized. These compounds seem to be in trivalent iron high-spin state in solvents such as chloroform, dichloromethane, benzene, and chlorobenzene, although their counter anion could not be detected by elemental analyses. They react with strong bases such as pyridine and imidazoles to form their mono- and subsequently their di-base complexes with formation constant of >106 and < 200 dm3 mol−1, respectively, in dichloromethane at 20 °C. The resultant mono-adducts appear to be trivalent iron low-spin while the di-base adducts are bivalent iron low-spin state complexes. The addition of ca. 10–30 equivalent of tetrabutylammonium-chloride or -bromide (electrolyte) to the solution containing FeTDPc or FeODPc, causes their spin-state change from iron(III) high to low-spin state. In a solid power state, however, both FeTDPc and FeODPc exist as a mixture of high-spin iron(III)- and intermediate-spin iron(II) species. Strangely, when these compounds are dissolved in polystyrene, i.e. each molecules are isolated from each other, the signals originated from the iron(II) component disappear.

Electron Transfer Induced by the Change of Spin States as a Catalytic Descriptor on C2N-TM Single-Atom Catalysts.

The catalytic activity and selectivity of metal single-atom catalysts strongly depend upon their spin states. However, their intrinsic connections are not yet clear. In this work, we evaluate the catalytic activity and selectivity of oxygen reduction reactions (ORRs) on C2N-supporting 3d transition metal (TM = Mn/Co/Ni/Cu) single-atom catalysts (SACs) using the density functional theory calculations. It is found that all of the SACs with different spin states tend to follow the 2e- H2O2 pathway, except for C2N-Mn (S = 1/2), which takes the 4e- OOH pathway. Interestingly, we found that the sum of the changes in the electron spin moments of the metal active centers and the reaction intermediate OOH affects the OOH electron transfer, and the electron transfer promotes the catalytic activity of the 2e- H2O2 pathway on C2N-TM SACs. Moreover, there is a strong linear relationship between the OOH electron transfer and the catalytic activity of the 2e- H2O2 pathway on C2N-TM SACs. These findings indicate that electron transfer induced by the change of spin states serves as a descriptor of the catalytic activity of the 2e- H2O2 pathway on C2N-TM SACs, which is very helpful for designing more powerful SACs.

Combining electron transfer, spin crossover, and redox properties in metal-organic frameworks

Hofmann coordination polymers (CPs) that couple the well-studied spin transition of the FeII central ion with electron-responsive ligands provide an innovative strategy toward multifunctional metal-organic frameworks (MOFs). Here, we developed a 2D planar network consisting of metal-cyanide-metal sheets in an unusual coordination mode, brought about by infinitely π-stacked redox-active bipyridinium derivatives as axial ligands. The obtained family of materials show vivid thermochromism attributed to electron transfer and/or electronic spin state change processes that can occur either independently or concomitantly. Importantly, the redox activity of the ligands within the structure leads to the quasi-reversible electrochemical reduction reaction on a spin-crossover complex at solid state. These observations have been confirmed via temperature-dependent single-crystal X-ray diffraction, magnetic measurements, Mössbauer, EPR, optical and vibrational spectroscopies as well as quantum chemical calculations.

Imaging Spin-Orbit Excitation of Yttrium through High-Energy Collisions with Rare Gas Atoms.

The energy required for spin-orbit excitation plays a critical role in understanding translational-to-electronic energy conversion, particularly in chemical reactions involving changes in spin states. This is particularly important for transition metal atoms possessing d-orbitals, which result in multiple spin-orbit split energy levels at low energies. The accurate identification and characterization of spin-orbit transitions in such species require advanced experimental techniques and theoretical support. In this study, the spin-orbit excited collisions of Y(2D3/2) with rare gas atoms Ne, Ar, and Kr leading to Y(2D5/2) were observed using laser-ablated crossed-beam and time-sliced ion velocity mapping imaging techniques. Through a comparison of the forward angular distributions of Y(2D3/2) to the backward and sideway scattering distributions of Y(2D5/2) from elastic and inelastic collisions of Y(2D) with rare gas atoms, this study reveals that the spin-orbit electronic excitation occurs with high collision energy and low impact parameters from backward and sideway collisions. The effectiveness of the spin-orbit excitation process is strongly dependent on the collision energy or temperature, suggesting that energy requirements of the process have to be considered in chemical reactions involving changes in spin states.

Leveraging electron spin driven photocatalytic hydrogen evolution ability of BiVO4 via crystal facet engineering and iron ion infiltration strategies

An electron spin regulated hydrogen evolution reaction (HER) for photocatalyst is significant to understand the underlying photocatalytic mechanism. Here, the iron with gradient distribution in BiVO4 can successfully activate HER of Fe-BiVO4. Mechanical performance calculations indicate that doped Fe3+ replacing V site can form stable chemical structure for BiVO4. Theoretical calculations suggest that the photo-generated electrons migrate from bulk to defect sites in surface layers of Fe-BiVO4. The doped Fe ions effectively improves the carrier transport ability and significantly reduces the carrier recombination probability. Electron spin state change of the 1Fe-BiVO4 (Mag) enhances evidently the current density in photocatalysis, and increases markedly the HER performance compared with that of 1Fe-BiVO4. More importantly, the magnetization further prolongs carrier lifetime and optimizes rate determining step free energy of water dissociation for Fe-BiVO4. Our work opens a new way to understand the effect of magnetic field controlling spin states on photocatalytic HER.

New Architecture Based on Metal-Organic Frameworks and Spin Crossover Complexes to Detect Volatile Organic Compounds.

We present here the encapsulation of a spin crossover complex C1 [FeII(L)] (L: 4-amino-, 2-(2-pyridinylmethylene)hydrazide) inside MOF-808(Zr), a chemically robust Metal-Organic Framework. The compound C1⊂MOF-808 retains its crystallinity as well as a partial porosity compared to pristine MOF and shows solvatochromism under Volatile Organic compounds (VOCs) sorption associated to a spin state change of the guest complex. More specifically, this compound shows an interesting reversible color change under formaldehyde and formic acid vapor sorption and can therefore be considered as a new kind of optical VOCs chemosensor, opening new doors for developing a broad range of VOCs optical sensors.

Ynamide and Azaalleneyl. Acid-Base Promoted Chelotropic and Spin-State Rearrangements in a Versatile Heterocumulene [(Ad)NCC(tBu)

We introduce the heterocumulene ligand [(Ad)NCC(tBu)]- (Ad=1-adamantyl (C10H15), tBu=tert-butyl, (C4H9)), which can adopt two forms, the azaalleneyl and ynamide. This ligand platform can undergo a reversible chelotropic shift using Brønsted acid-base chemistry, which promotes an unprecedented spin-state change of the [VIII] ion. These unique scaffolds are prepared via addition of 1-adamantyl isonitrile (C≡NAd) across the alkylidyne in complexes [(BDI)V≡CtBu(OTf)] (A) (BDI-=ArNC(CH3)CHC(CH3)NAr), Ar=2,6-iPr2C6H3) and [(dBDI)V≡CtBu(OEt2)] (B) (dBDI2-=ArNC(CH3)CHC(CH2)NAr). Complex A reacts with C≡NAd, to generate the high-spin [VIII] complex with a κ1-N-ynamide ligand, [(BDI)V{κ1-N-(Ad)NCC(tBu)}(OTf)] (1). Conversely, B reacts with C≡NAd to generate a low-spin [VIII] diamagnetic complex having a chelated κ2-C,N-azaalleneyl ligand, [(dBDI)V{κ2-N,C-(Ad)NCC(tBu)}] (2). Theoretical studies have been applied to better understand the mechanism of formation of 2 and the electronic reconfiguration upon structural rearrangement by the alteration of ligand denticity between 1 and 2.

Full-waveform tomography reveals iron spin crossover in Earth’s lower mantle

Three-dimensional models of Earth’s seismic structure can be used to identify temperature-dependent phenomena, including mineralogical phase and spin transformations, that are obscured in 1-D spherical averages. Full-waveform tomography maps seismic wave-speeds inside the Earth in three dimensions, at a higher resolution than classical methods. By providing absolute wave speeds (rather than perturbations) and simultaneously constraining bulk and shear wave speeds over the same frequency range, it becomes feasible to distinguish variations in temperature from changes in composition or spin state. We present a quantitative joint interpretation of bulk and shear wave speeds in the lower mantle, using a recently published full-waveform tomography model. At all depths the diversity of wave speeds cannot be explained by an isochemical mantle. Between 1000 and 2500 km depth, hypothetical mantle models containing an electronic spin crossover in ferropericlase provide a significantly better fit to the wave-speed distributions, as well as more realistic temperatures and silica contents, than models without a spin crossover. Below 2500 km, wave speed distributions are explained by an enrichment in silica towards the core-mantle boundary. This silica enrichment may represent the fractionated remains of an ancient basal magma ocean.

Soluble molecular switches in electrospun nanofibers

Compounds that exhibit the spin crossover effect are known to show a change of spin states through external stimuli. This reversible switching of spin states is accompanied by a change of the properties of the compound. Complexes, like iron (II)-triazole complexes, that exhibit this behavior at ambient temperature are often discussed for potential applications. In previous studies we synthesized iron (II)-triazole complexes and implemented them into electrospun nanofibers. We used Mössbauer spectroscopy in first studies to prove a successful implementation with maintaining spin crossover properties. Further studies from us showed that it is possible to use different electrospinning methods to either do a implementation or a deposition of the synthesized solid SCO material into or onto the polymer nanofibers. We now used a solvent in which both, the used iron (II)-triazole complex [Fe(atrz)3](2 ns)2 and three different polymers (Polyacrylonitrile, Polymethylmethacrylate and Polyvinylpyrrolidone), are soluble. This shall lead to a higher homogeneous distribution of the complex along the nanofibers. Mössbauer spectroscopy and other measurements are therefore in use to show a successful implementation without any significant changes to the complex.

Changes in aromaticity of spin-crossover complexes: a signature for non-innocent ligands.

The influence of the spin state of the metal centre in spin crossover compounds on the aromaticity of the ligands has been investigated for iron(II)tris-bipyridine (Fe(bpy)32+), and Fe(II)(formazanate)2 (as a truncated model and the full phenyl substituted compound). It was found that the aromaticity of the bipyridine ligands is unaffected by changing the spin state of the central iron atom, but that of the formazanate ligands is reduced upon transition to the high-spin state. This change in aromaticity is rationalized using the symmetry selection rules for aromaticity in terms of virtual excitations from occupied to empty orbitals. A further consequence of this loss in aromaticity is a shift to higher energy in the ring vibrations of the formazanate compounds that can be observed in either its IR or Raman spectrum; this prediction has been confirmed here. This change in aromaticity as a consequence of change in spin state can be regarded as an indication for non-innocent ligands.

Hydrogen-designed spin-states of 2D silicon carbide and graphene nanostructures.

Identifying and manipulating spin in two-dimensional materials is of great interest in advancing quantum information and sensing technologies, as well as in the development of spintronic devices. Here, we investigate the influence of hydrogen adsorption on the electronic and magnetic properties of graphene-like triangulenes. We have constructed triangulenes from SiC monolayers, which have been successfully synthesized very recently, extending our investigation to include graphene triangulenes. This advancement in the synthesis of SiC monolayers allows us to investigate deeper into the unique properties of SiC-based triangulenes and compare them with their graphene counterparts. The addition of hydrogen has been found to induce a magnetic moment in the SiC monolayer, with a more localized spin density when H is adsorbed in the C sites while spreading through the lattice when adsorbed on the Si sites. In triangular flakes, the ground spin state changes with the adsorption site: decreasing multiplicity on edge-defined sublattices and increasing it on the opposite sublattice. These findings suggest hydrogen adsorption as a tool for tuning spin-state properties in SiC and graphene nanostructures, with potential applications in spintronics and spin quantum dot devices.

Low-spin to low-spin valence tautomeric transition in cobalt bis-dioxolenes.

Cobalt dioxolenes are a well-known class of switchable coordination compounds showing intramolecular electron transfer, which is always accompanied by a spin state change at the cobalt center. Here, we present the first example of thermally switchable cobalt bis-dioxolenes where intramolecular electron transfer seems to take place, but the spin state change is suppressed. This leads to the detection of thermal transition between a common ls-CoIII(SQ˙-)(Cat2-) and an extremely rare ls-CoII(SQ˙-)2 electronic state (hs - high-spin, ls - low-spin, SQ˙- - benzosemiquinonate(1-) radical and Cat2- - catecholate(2-)). Parallel to the present work, a similar work but on cobalt mono-dioxolenes has just appeared (Chem. Eur. J., 2023, 29, e202300091), suggesting thermal transition between ls-CoIII(Cat2-) and ls-CoII(SQ˙-) electronic states.

Structural engineering of atomic catalysts for electrocatalysis.

As a burgeoning category of heterogeneous catalysts, atomic catalysts have been extensively researched in the field of electrocatalysis. To satisfy different electrocatalytic reactions, single-atom catalysts (SACs), diatomic catalysts (DACs) and triatomic catalysts (TACs) have been successfully designed and synthesized, in which microenvironment structure regulation is the core to achieve high-efficiency catalytic activity and selectivity. In this review, the effect of the geometric and electronic structure of metal active centers on catalytic performance is systematically introduced, including substrates, central metal atoms, and the coordination environment. Then theoretical understanding of atomic catalysts for electrocatalysis is innovatively discussed, including synergistic effects, defect coupled spin state change and crystal field distortion spin state change. In addition, we propose the challenges to optimize atomic catalysts for electrocatalysis applications, including controlled synthesis, increasing the density of active sites, enhancing intrinsic activity, and improving the stability. Moreover, the structure-function relationships of atomic catalysts in the CO2 reduction reaction, nitrogen reduction reaction, oxygen reduction reaction, hydrogen evolution reaction, and oxygen evolution reaction are highlighted. To facilitate the development of high-performance atomic catalysts, several technical challenges and research orientations are put forward.