Coordination-induced Spin-state Switching Research Articles

Spin-State Control in Dysprosium(III) Metallacrown Magnets via Thioacetal Modification.

Integrating controllable spin states into single-molecule magnets (SMMs) enables precise manipulation of magnetic interactions at a molecular level, but remains a synthetic challenge. Herein, we developed a 3d-4f metallacrown (MC) magnet [DyNi5(quinha)5(Clsal)2(py)8](ClO4)∙4H2O (H2quinha = quinaldichydroxamic acid, HClsal = 5-chlorosalicylaldehyde) wherein a square planar NiII is stabilized by chemical stacking. Thioacetal modification was employed via post-synthetic ligand substitutions and yielded [DyNi5(quinha)5(Clsaldt)2(py)8](ClO4)·3H2O (HClsaldt = 4-chloro-2-(1,3-dithiolan-2-yl)phenol). Thanks to the additional ligations of thioacetal onto the NiII site, coordination-induced spin state switching (CISSS) took place with spin state altering from low-spin S = 0 to high-spin S = 1. The synergy of CISSS effect and magnetic interactions results in distinct energy splitting and magnetic dynamics. Magnetic studies indicate prominent enhancement of reversal barrier from 57 cm-1 to 423 cm-1, along with hysteresis opening and an over 200-fold increment in coercive field at 2 K. Ab initio calculations provide deeper insights into the exchange models and rationalize the relaxation/tunnelling pathways. These results demonstrate here provide a fire-new perspective in modulating the magnetization relaxation via the incorporation of controllable spin states and magnetic interactions facilitated by the CISSS approach.

Spin‐State Control in Dysprosium(III) Metallacrown Magnets via Thioacetal Modification

Integrating controllable spin states into single‐molecule magnets (SMMs) enables precise manipulation of magnetic interactions at a molecular level, but remains a synthetic challenge. Herein, we developed a 3d‐4f metallacrown (MC) magnet [DyNi5(quinha)5(Clsal)2(py)8](ClO4)∙4H2O (H2quinha = quinaldichydroxamic acid, HClsal = 5‐chlorosalicylaldehyde) wherein a square planar NiII is stabilized by chemical stacking. Thioacetal modification was employed via post‐synthetic ligand substitutions and yielded [DyNi5(quinha)5(Clsaldt)2(py)8](ClO4)·3H2O (HClsaldt = 4‐chloro‐2‐(1,3‐dithiolan‐2‐yl)phenol). Thanks to the additional ligations of thioacetal onto the NiII site, coordination‐induced spin state switching (CISSS) took place with spin state altering from low‐spin S = 0 to high‐spin S = 1. The synergy of CISSS effect and magnetic interactions results in distinct energy splitting and magnetic dynamics. Magnetic studies indicate prominent enhancement of reversal barrier from 57 cm−1 to 423 cm−1, along with hysteresis opening and an over 200‐fold increment in coercive field at 2 K. Ab initio calculations provide deeper insights into the exchange models and rationalize the relaxation/tunnelling pathways. These results demonstrate here provide a fire‐new perspective in modulating the magnetization relaxation via the incorporation of controllable spin states and magnetic interactions facilitated by the CISSS approach.

Binucleating Jäger-type {(N2O2)2}4- ligands: magnetic and electronic interactions of Fe(II), Ni(II) and Cu(II) across an in-plane TTF-bridge.

The simultaneous presence of different electrophores provides an interesting playground for responsive materials. Herein, we present the incorporation of a twice-reversibly oxidizable tetrathiafulvalene (TTF) unit into a binucleating ligand, bridging two metal centers in a fully conjugated plane. A two-step synthesis scheme gave the D2h symmetric Schiff base-like ligand H4L in moderate yields from which the corresponding copper(II) [Cu2L], nickel(II) [Ni2L], [Ni2L(py)4] and iron(II) complexes [Fe2L(py)4], [Fe2L(dmap)4] and [Fe2L(bpee)2]·1 Tol could be obtained. Characterization was performed through 1H-NMR, IR, UV-vis and 57Fe-Mössbauer spectroscopy, SQUID magnetometry and cyclic voltammetry, supported by density functional theory (DFT) calculations. Single crystal X-ray analysis of [Ni2L(py)4] revealed six-coordinate paramagnetic centers, whereas [Ni2L] underwent gradual coordination induced spin state switching (CISSS) in solution. The magnetic independence of both metal centers is echoed by close-to-ideal Curie-plots of the [Cu2L] system and the gradual spin crossover of all iron(II) compounds. By contrast, cyclic voltammetry measurements in solution indicated oxidation-dependent TTF-metal interactions, as well as metal-metal interactions. The reversible TTF-borne events in H4L and [Ni2L] are overlaid with metal-borne events in the case of [Fe2L(py)4], as is corroborated by an analysis of the frontier orbital landscapes and through diagnostic spectral features upon chemical oxidation.

Proton‐Induced Spin State Switching in an FeIII Complex

AbstractReversible proton‐induced spin state switching of an FeIII complex in solution is observed at room temperature. A reversible magnetic response was detected in the complex, [FeIII(sal2323)]ClO4 (1), using Evans’ method 1H NMR spectroscopy which indicated cumulative switching from low‐spin to high‐spin upon addition of one and two equivalents of acid. Infrared spectroscopy suggests a coordination‐induced spin state switching (CISSS) effect, whereby protonation displaces the metal‐phenoxo donors. The analogous complex, [FeIII(4‐NEt2‐sal2323)]ClO4 (2), with a diethylamino group on the ligand, was used to combine the magnetic change with a colorimetric response. Comparison of the protonation responses of 1 and 2 reveals that the magnetic switching is caused by perturbation of the immediate coordination sphere of the complex. These complexes constitute a new class of analyte sensor which operate by magneto‐modulation, and in the case of 2, also yield a colorimetric response.

Proton-Induced Spin State Switching in an FeIII Complex.

Reversible proton-induced spin state switching of an FeIII complex in solution is observed at room temperature. A reversible magnetic response was detected in the complex, [FeIII (sal2 323)]ClO4 (1), using Evans' method 1 H NMR spectroscopy which indicated cumulative switching from low-spin to high-spin upon addition of one and two equivalents of acid. Infrared spectroscopy suggests a coordination-induced spin state switching (CISSS) effect, whereby protonation displaces the metal-phenoxo donors. The analogous complex, [FeIII (4-NEt2 -sal2 323)]ClO4 (2), with a diethylamino group on the ligand, was used to combine the magnetic change with a colorimetric response. Comparison of the protonation responses of 1 and 2 reveals that the magnetic switching is caused by perturbation of the immediate coordination sphere of the complex. These complexes constitute a new class of analyte sensor which operate by magneto-modulation, and in the case of 2, also yield a colorimetric response.

Chemically and Light-Driven Coordination-Induced Spin State Switching (CISSS) of a nonheme-iron complex

Abstract The new Fe(II) complex [Fe(trident)(bmik)](ClO4)2 (1) (trident = bis(2-pyridylmethyl)benzylamine and bmik = bis(1-methylimidazole)ketone) exhibits a change of magnetic moment in dichloromethane (DCM) solution upon addition of pyridine which is attributed to the Coordination-Induced Spin State Switching effect (CISSS). By attaching a photoisomerizable azopyridine sidegroup to the tridentate ligand the complex [Fe(azpy-trident)(bmik)](ClO4)2 (2; azpy-trident = [N,N-bis(2-pyridylmethyl)]-3-(3-pyridylazo)benzylamine) is obtained. As detected by Evans NMR spectroscopy, 2 reversibly changes its magnetic moment in homogeneous solution upon photoirradiation which is attributed to intermolecular Light-Driven Coordination-Induced Spin State Switching (LD-CISSS). Further support for this interpretation is inferred from concentration-dependent Evans NMR measurements.

Vapor-triggered reversible crystal transformation of a nickel-based magnetic molecular switch.

Vapor-triggered crystal-to-crystal transformation between a discrete trinuclear complex [Ni3(sih)2(py)8] and a two-dimensional (2D) coordination polymer [Ni3(sih)2(py)2]n·2DMF·2H2O was demonstrated. It provides an example of a solid-state coordination-induced spin state switch behavior attributed to the structural phase transition triggered by solvent signal. The reversible nature can be detected by both optical (spectral) and magnetic responses in cycles.

Towards Photoswitchable Contrast Agents for Absolute 3D Temperature MR Imaging

Temperature can be used as clinical marker for tissue metabolism and the detection of inflammations or tumors. The use of magnetic resonance imaging (MRI) for monitoring physiological parameters like the temperature noninvasively is steadily increasing. In this study, we present a proof‐of‐principle study of MRI contrast agents (CA) for absolute and concentration independent temperature imaging. These CAs are based on azoimidazole substituted NiII porphyrins, which can undergo Light‐Driven Coordination‐Induced Spin State Switching (LD‐CISSS) in solution. Monitoring the fast first order kinetic of back isomerisation (cis to trans) with standard clinical MR imaging sequences allows the determination of half‐lives, that can be directly translated into absolute temperatures. Different temperature responsive CAs were successfully tested as prototypes in methanol‐based gels and created temperature maps of gradient phantoms with high spatial resolution (0.13×0.13×1.1 mm) and low temperature errors (<0.22 °C). The method is sufficiently fast to record the temperature flow from a heat source as a film.

A Fluorescence-Detected Coordination-Induced Spin State Switch.

The response of the spin state to in situ variation of the coordination number (CISSS) is a promising and viable approach to smart sensor materials, yet it suffers to date from insensitive detection. Herein, we present the synthetic access to a family of planar nickel(II) complexes, whose CISSS is sensitively followed by means of fluorescence detection. For this purpose, nickel(II) complexes with four phenazine-based Schiff base-like ligands were synthesized and characterized through solution-phase spectroscopy (NMR and UV-vis), solid-state structure analysis (single-crystal XRD), and extended theoretical modeling. All of them reveal CISSS in solution through axial ligating a range of N- and O-donors. CISSS correlates nicely with the basicity of the axial ligand and the substitution-dependent acidity of the nickel(II) coordination site. Remarkably, three out of the four nickel(II) complexes are fluorescent in noncoordinating solvents but are fluorescence-silent in the presence of axial ligands such as pyridine. As these complexes are rare examples of fluorescent nickel(II) complexes, the photophysical properties with a coordination number of 4 were studied in detail, including temperature-dependent lifetime and quantum yield determinations. Most importantly, fluorescence quenching upon adding axial ligands allows a "black or white", i.e. digital, sensoring of spin state alternation. Our studies of fluorescence-detected CISSS (FD-CISSS) revealed that absorption-based CISSS and FD-CISSS are super proportional with respect to the pyridine concentration: FD-CISSS features a higher sensitivity. Overall, our findings indicate a favored ligation of these nickel(II) complexes in the excited state in comparison to the ground state.

Acidity-Driven Bidirectional Room-Temperature Spin-State Switch and Fluorescence Modulation of a Mononuclear Fe(II) Complex

Room-temperature switchable materials showing multiple responses toward external stimuli are highly desired. Herein, we report bidirectional spin-state switch and fluorescence modulation of an Fe(I...

Interplay of Spin Crossover and Coordination-Induced Spin State Switch for Iron Bis(pyrazolyl)methanes in Solution.

Bis(pyrazolyl)bipyridinylmethane iron(II) complexes show a versatile spin state switching behavior in different solvents. In the solid, the magnetic properties of the compounds have been characterized by X-ray diffraction, Mößbauer spectroscopy, and SQUID magnetometry and point toward a high spin state. For nitrilic solvents, the solvation of the complexes leads to a change of the coordination environment from {N5O} to {N6} and results in a temperature-dependent SCO behavior. Thermodynamic properties of this transformation are obtained via UV/vis spectroscopy, SQUID measurements, and the Evans NMR method. Moreover, a coordination-induced spin state switch (CISSS) to low spin is observed by using methanol as solvent, triggered through a rearrangement of the coordination sphere. The same behavior can be observed by changing the stoichiometry of the ligand-to-metal ratio in MeCN, where the process is reversible. This transformation is monitored via UV/vis spectroscopy, and the resulting new bis-meridional coordination motif, first described for bis(pyrazolyl)methanes, is characterized in the solid state via X-ray diffraction, Mößbauer spectroscopy, and SQUID measurements. The sophisticated correlation of these switchable properties in dependence on different types of solvents reveals that the influence of the solvent on the coordination environment and magnetic properties should not be underestimated. Furthermore, careful investigation is necessary to differentiate between a thermally-induced spin crossover and a coordination-induced spin state switch.

Ni(II)porphyrins as pH dependent light-driven coordination-induced spin-state switches (LD-CISSS) in aqueous solution

A water-soluble Ni(II)-porphyrin substituted with a covalently attached azopyridine ligand was synthesized. Upon irradiation with violet and green light, the azo unit performs a reversible cis–trans isomerization. This geometry change triggers a coordination/de-coordination of the pyridine nitrogen at the central nickel(II) ion. The concomitant change in coordination number at the Ni ion in turn switches the spin state between high and low spin, a process we coined a “light-driven coordination-induced spin state switch (LD-CISSS). To increase the coordination power of the pyridine, particularly in aqueous environments, we introduced an electron donating OH group in 4-position. With increasing pH, the hydroxyl group is deprotonated, further enforcing coordination. We report on the properties of this pH-dependent spin switch, particularly the magnetic properties.

Reversible coordination-induced spin-state switching in complexes on metal surfaces.

Molecular spin switches are attractive candidates for controlling the spin polarization developing at the interface between molecules and magnetic metal surfaces1,2, which is relevant for molecular spintronics devices3-5. However, so far, intrinsic spin switches such as spin-crossover complexes have suffered from fragmentation or loss of functionality following adsorption on metal surfaces, with rare exceptions6-9. Robust metal-organic platforms, on the other hand, rely on external axial ligands to induce spin switching10-14. Here we integrate a spin switching functionality into robust complexes, relying on the mechanical movement of an axial ligand strapped to the porphyrin ring. Reversible interlocked switching of spin and coordination, induced by electron injection, is demonstrated on Ag(111) for this class of compounds. The stability of the two spin and coordination states of the molecules exceeds days at 4 K. The potential applications of this switching concept go beyond the spin functionality, and may turn out to be useful for controlling the catalytic activity of surfaces15.

Coordination‐Induced Spin‐State Switching of an Aminyl‐Radical‐Bridged Nickel(II) Porphyrin Dimer between Doublet and Sextet States

A bis(NiII -porphyrinyl)aminyl radical with meso-C6 F5 groups was prepared as a spin-delocalized stable aminyl radical with a doublet spin state. Upon addition of pyridine, both NiII centers became hexacoordinated by accepting two axial pyridines, which triggered a spin-state change of the NiII centers from diamagnetic (S=0) to paramagnetic (S=1). The resulting high-spin NiII centers interact with the aminyl radical ferromagnetically to give rise to an overall sextet state (S=5/2). Importantly, this coordination-induced spin-state switching can be conducted in a reversible manner, in that washing of the high-spin radical with aqueous hydrochloric acid regenerates the original doublet radical in good yield.

Coordination‐Induced Spin‐State Switching with Nickel(II) salpn Complexes: Electronic versus Steric Effects and Influence of Intermolecular Interactions

Four nickel(II) salpn (salicylidenepropylene iminate) complexes are investigated concerning their capability to perform CISSS (coordination‐induced spin‐state switching). To this end, pyridine titration experiments are performed with the nickel salpn complexes [Ni(salpn)], [Ni(salpntBuCF3)], [Ni(salpnCF3)] and [Ni(salpnSbenz)]. The electronic‐structural changes are monitored by UV/Vis spectroscopy and Evans NMR spectroscopy. Association constants (K1s and K2), as well as thermodynamic parameters (ΔH, ΔS, and ΔG), for the binding of pyridine are determined. In comparison with porphyrins and porphyrin‐derived systems investigated earlier, the salpn systems exhibit quite different coordination properties. In particular, the fluorinated systems show the formation of dimers due to CH–π and π–π stacking. On the other hand, the investigated compounds coordinate axial ligands with affinities comparable with those of the porphyrin‐based analogs. This renders them eligible for the preparation of LD‐CISSS (light‐driven CISSS) systems, which, in turn, may be applied as functional MRI contrast agents.

Synthesis and Optical Properties of Phenanthroline-Derived Schiff Base-Like Dinuclear RuII -NiII Complexes.

Two phenanthroline-derived Schiff base-like ligands with a covalently linked ruthenium(II) phosphorescent unit were synthesised and converted into bimetallic RuII -NiII complexes. The optical properties were studied to examine a possible photoluminescence quenching through a nonradiative energy-transfer upon a coordination-induced spin-state switch (CISSS) at the nickel(II) centre. Therefore, the metalloligands and the nickel(II) complexes were studied using UV/Vis absorbance, steady-state, and time-resolved emission spectroscopy in solutions of MeCN and pyridine. It is demonstrated that the nature of the bridging ligand between the ruthenium(II) donor and the nickel(II) acceptor strongly influences the photophysical behaviour upon CISSS. For the complex with a phenazine bridge, photoluminescence quenching is observed in the presence of a paramagnetic nickel(II) centre.

Switching Magnetic Properties by a Mechanical Motion

Switching magnetic properties have attracted a wide interest from inorganic chemist for the objectives of information storage and quantum computing at the molecular level. This review is focused on magnetic switches based on a mechanical motion, which is an innovative approach. Three main strategies to control magnetic properties by a mechanical motion have been developed in the literature and will be described. The first one (ligand-induced spin change) consists in modulating the ligand field strength by a configuration change of the ligand in spin-crossover complexes. The second one (coordination-induced spin-state switching) is based on a change in the coordination number of a metallic center that is triggered by the motion of one ligand. The third one uses the modulation of the exchange interaction between two spin-centers by a mechanical motion.

Design, synthesis, and evaluation of nickel dipyridylmethane complexes for Coordination-Induced Spin State Switching (CISSS).

In order to develop a new system capable of performing Ligand-Driven Coordination-Induced Spin State Switching (LD-CISSS), a new CISSS complex based on a nickel(ii) dipyridylmethane framework was rationally designed, synthesized, and investigated both experimentally and theoretically. In DFT calculations, a dipyridylmethane dicarboxylic acid ligand was determined to be most suitable for this purpose. The corresponding nickel(ii) complex was synthesized by an optimized procedure, and the CISSS effect was evidenced by crystallography as well as Evans NMR susceptibility measurements. In the solid state, the square planar nickel complex is diamagnetic and the octahedral bispyridine adduct is paramagnetic. Also, a dimer containing three ethanol ligands was obtained. Dimer formation occurs in solution as well. Upon addition of pyridine, a continuous transition from predominantly diamagnetic to paramagnetic behavior takes place. Equilibrium constants for the binding of pyridine as well as corresponding thermodynamic parameters indicate a high affinity for this ligand and show that the title system is a suitable candidate for LD-CISSS.

Design and Synthesis of Photodissociable Ligands Based on Azoimidazoles for Light-Driven Coordination-Induced Spin State Switching in Homogeneous Solution

Light-switchable azoimidazoles were rationally designed and synthesized, and their performance was investigated as photodissociable ligands (PDL) and for spin state switching of Ni porphyrins. The rationally designed ligands exhibit a high photochemical conversion rate (trans → cis > 98%) and no measurable fatigue over a large number of switching cycles at room temperature under air. As compared to the known phenylazopyridines, the phenylazoimidazoles exhibit a much stronger affinity as axial ligands to Ni porphyrin in the binding trans configuration and a low affinity in their cis form. This affinity switching was used to control the coordination number of Ni(2+). Concomitant with the change in coordination number is the change of the spin state from triplet (high spin) to singlet state (low spin). We report on phenylazoimidazole-based PDLs that switch the paramagnetic ratio of the investigated nickel species by up to 70%. Consequently, azoimidazoles exhibit considerably higher switching efficiencies than previously described pyridine-based PDLs.

Coordination-induced spin-state switching with nickel chlorin and nickel isobacteriochlorin.

We present the first coordination-induced spin-state switching with nickel chlorin and nickel isobacteriochlorin. The spin-state switching was monitored by UV-vis spectroscopy and NMR titration experiments. The association constants (K1 and K2) and thermodynamic parameters (ΔH and ΔS) of the coordination of pyridine were determined. The first X-ray analyses of a paramagnetic nickel chlorin and a nickel isobacteriochlorin provide further information about the structure of the octahedral complexes. Nickel chlorin and even more pronounced nickel isobacteriochlorin exhibit stronger coordination of axial ligands compared to the corresponding nickel porphyrin and thus provide the basis for more efficient spin-switching systems.