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Responsive spin-crossover (SCO) metal-organic cages (MOCs) are emerging dynamic platforms with potential for advanced applications in magnetic sensing and molecular switching. Among these, FeIII-based MOCs are particularly noteworthy for their air stability, yet they remain largely unexplored. Herein, we report the synthesis of two novel FeIII MOCs using a bis-bidentate ligand approach, which exhibit SCO activity above room temperature. These represent the first SCO-active FeIII cages and feature an atypical {FeN6}-type coordination sphere, uncommon for FeIII SCO compounds. Our study reveals that these MOCs are sensitive to acid/base variations, enabling reversible magnetic switching in solution. The presence of multiple active proton sites within these SCO-MOCs facilitates multisite, multilevel proton-induced spin-state modulation. This behavior is observed at room temperature through 1H NMR spectroscopy, capturing the subtle proton-induced spin-state transitions triggered by pH changes. Further insights from extended X-ray absorption fine structure (EXAFS) and theoretical analyses indicate that these magnetic alterations primarily result from the protonation and deprotonation processes at the NH active sites on the ligands. These processes induce changes in the secondary coordination sphere, thereby modulating the magnetic properties of the cages. The capability of these FeIII MOCs to integrate magnetic responses with environmental stimuli underscores their potential as finely tunable magnetic sensors and highlights their versatility as molecular switches. This work paves the way for the development of SCO-active materials with tailored properties for applications in sensing and molecular switching.
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Pyroelectric materials hold significant potential for energy harvesting, sensing, and imaging applications. However, achieving high-performance pyroelectricity across a wide temperature range near room temperature remains a significant challenge. Herein, we demonstrate a single crystal of Fe(II) spin-crossover compound shows remarkable pyroelectric properties accompanied by a thermally controlled spin transition. In this material, the uniaxial alignment of polar molecules results in a polarization of the lattice. As the molecular geometry is modulated during a gradual spin transition, the polar axis experiences a colossal thermal expansion with a coefficient of 796×10-6â K-1. Consequently, the material's polarization undergoes significant modulation as a secondary pyroelectric effect. The considerable shift in polarization (pyroelectric coefficient, p=3.7-22â nC K-1cm-2), coupled with a low dielectric constant (ϵ'=4.4-5.4) over a remarkably wide temperature range of 298 to 400â K, suggests this material is a high-performance pyroelectric. The demonstration of pyroelectricity combined with magnetic switching in this study will inspire further investigations in the field of molecular electronics and magnetism.
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A mononuclear valence tautomeric (VT) complex, [Co(pycz)2(Sq)(Cat)] (1-trans), where pycz = 9-(pyridin-4-yl)-9H-carbazole, Sqâ - = 3,5-di-tert-butyl-semiquinonato, and Cat2- = 3,5-di-tert-butyl-catecholato, is synthesized in the trans configuration, which undergoes one-step valence tautomeric transition above room temperature. Remarkably, 1-trans can transform into its isomeric structure, [Co(pycz)2(Sq)(Sq)] (1-cis), at temperature above 350â K in a single-crystal-to-single-crystal way by in situ molecular twist, and the resulting 1-cis exhibits a pronounced two-step VT transition during magnetic measurements that is rare for mononuclear VT complexes. Such drastic solid-state structural transformation is reported in VT compounds for the first time, which is actuated by a crystal surface's melting-recrystallization induced phase transition process. DFT calculations offer an underlying mechanism suggesting a concerted bond rotation during the structural transformation. The results demonstrate an unconventional approach that realizes structural transformation of VT complexes and the control of VT performance.
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Controlling molecular chirality by external stimuli is of great significance in both fundamental research and technological applications. Herein, we report a high-temperature (384 K) molecular ferroelectric of a Cu(II) complex whose spontaneous polarization can be switched associated with flipping of molecular chirality. In this two-dimensional perovskite structure, the inorganic layer is separated by (NH3(CH2)2SS(CH2)2NH3)2+ organic cations skewed in a chiral conformation (P- or M-helicity in an individual crystal). As the stereodynamic disulfide bridge determines the molecular dipole moment along the polar axis, the chiral organic cation can be converted to its enantiomer as a consequence of an electric field-induced shift of the S-S moiety relative to its screw axis during the ferroelectric switching. The variation of the molecular chirality is examined with single-crystal X-ray diffraction and circular dichroism spectra. The simultaneous switching of molecular chirality and spontaneous polarization in this perovskite ferroelectric may lead to novel chiral electronic phenomena.
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In the past two decades, numerous molecular ferroelectrics have been reported. However, metal-free molecular ferroelectrics with high working temperatures and large spontaneous polarizations are still uncommon. Herein, we present two metal-free molecular ferroelectrics prepared from monoprotonated hexamethylenetetramine (HMTA), namely (HMTAH)Cl and (HMTAH)Br, which crystallize in a polar point group of 3m. In these crystals, the polar HMTAH+ organic cations can be reoriented 180° along the polar axis because of the quasispherical molecular geometry. As a result of the large shift of the positively charged protonated N atoms, these compounds demonstrate large spontaneous polarizations with values of 8.3 and 8.1 µC cm-2 and high working temperatures of 390 and 435 K, respectively. The ferroelectric property of these compounds is characterized with second-harmonic generation, ferroelectric hysteresis loop, and pyroelectric current measurements.
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Numerous Fe(II) spin-crossover (SCO) compounds have been developed in the past decades, while the reports on the SCO materials with halogen atoms acting as coordinating ligands remain rare. In this study, we synthesize three iron(II) halide complexes with a general formula of [FeII(Py5Me2)X]+ (Py5Me2 = 2,6-bis[1,1-bis(2-pyridyl)ethyl]pyridine, X = Cl- or Br-) that undergo complete SCO transitions at near room temperature. The SCO properties of these compounds are investigated in detail by magnetic measurements, variable-temperature single-crystal X-ray diffractions, and Mössbauer spectra analyses. Because of the good stability of the coordination structures and suitable ligand-field strength, these compounds show robust spin transitions in both solid state and solution.
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Multifunctional materials with switchable magnetic and dielectric properties are crucial for the development of memory and sensor devices. Herein, we report a methoxy-bridged dinuclear iron-pyridyl complex [Fe2(4-picoline)4(NCS)4(µ-OCH3)2] (1), which shows simultaneous thermal-induced magnetic and dielectric switchings. Within the phase-transition temperature range, both magnetic switching and the dielectric anomaly were detected, in which the thermal hysteresis loops were 23 and 21 K, respectively. Detailed structural analyses revealed that these simultaneous switchings were rooted in the flexible rotatable ligands, which were actuated by readjusting the π-π intermolecular interactions between the pyridine ligands in the trans positions of the metal centers. These results were comprehensively investigated both experimentally and theoretically. This study presents a new guideline to control both the magnetic and dielectric properties of molecular complexes by external stimuli.
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The molecular crystals that manifest unusual mechanical properties have attracted growing attention. Herein, we prepared an organic single crystal that shows bidirectional superelastic transformation in response to shear stress. Single-crystal X-ray diffractions revealed this crystal-twinning related shape change is owed to a stress-controlled 90° rotation of 4,4'-bipyridine around the hydrogen bonds of a chiral organic trimer. As a consequence of the 90° shift in the aromatic plane, an interconversion of crystallographic a-, b-axes (aâb' and bâa') was detected. The molecular rotations changed the anisotropic absorption of linearly polarized light. Therefore, a stress-induced inversion of linear dichroism spectra was demonstrated for the first time. This study reveals the superior mechanical flexibilities of single crystals can be realized by harnessing the molecular rotations and this superelastic crystal may find applications in optical switching and communications.
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A two-dimensional grid-like coordination polymer, [Fe(NCBH3)2(Py2ttz)2]·4CHCl3 (1·4CHCl3, Py2ttz = 2,5-di(pyridin-4-yl)thiazolo[5,4-d]thiazole), showed one-step complete spin crossover with unexpectedly large hysteresis loop of 64 K wide and temperature-induced excited spin-state trapping effect below 91 K.
RESUMO
Two isostructural valence tautomeric (VT) complexes with different critical temperatures were prepared and fully investigated through a series of magnetic, structural, spectral, and differential scanning calorimetry evidence. The kinetic effect in the VT complex was observed for the first time through scan-rate-dependent studies and further validated by annealing tests.
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Halogen-substituted Fe(III) compounds, [Fe(HphsalpmX)2]PTFB (HphsalpmX = 5-X-(R,S)-((phenyl(2-pyridyl)methylimino)methyl)phenol, PTFB = phenyltrifluoroborate; X = F for 1, Cl for 2, Br for 3) and [Fe(HphsalpmX)2]PTFB·MeOH (X = I for 4·MeOH), were synthesized. Compounds 1, 4·MeOH, and its desolvated form 4 exhibited an invariant high-spin state in the whole temperature range, while 2 and 3 underwent gradual, nonhysteretic, and incomplete spin crossover (SCO) with transition temperatures (TC) of 153 and 220 K, respectively. Interestingly, the SCO-active compounds 2 and 3 showed light-induced excited spin-state trapping (LIESST) effects at 10 K, and light-induced reversible ON/OFF switching behaviors were realized by alternately using 880 and 1064 nm light, while the thermally inert compound 4·MeOH unexpectedly showed a reverse-LIESST effect. These results may help to design and synthesize new photoresponsive SCO Fe(III) compounds for the development of switchable materials.
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Materials that demonstrate a multichannel controllable color change in response to external stimuli are fascinating for their potential applications in sensoring and displaying devices. Herein we report a FeII spin-crossover (SCO) compound that exhibits both solvatochromism and thermochromism under an ambient environment. This Hofmann-type compound possesses two different pores where the solvent guests can be removed in a two-step process. Because the loss of solvent guests modifies the spin state of magnetic centers, an unusual yellow-red-yellow two-step color change of crystals was detected. Moreover, because of the strong cooperativity of the spin centers, a dramatic red-to-yellow color change of crystals in response to a minute thermal perturbation around 303 K is triggered by an abrupt spin transition of the metal centers. The multichannel controllable dramatic color change demonstrated in the present compound highlights the sensoring and displaying roles of SCO materials.
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Two organic-inorganic hybrid complexes, (CH3NH3)Na[Fe(CN)5NO]·H2O (1) and (CH3NH3)2[Fe(CN)5NO] (2), which exhibit stepwise dielectric switching as well as photo-induced structural transformation, are synthesized and examined. In these two compounds, the photo-responsive complex anions, [Fe(CN)5NO]2-, connected by Na+ through N-Na coordination bonds or CH3NH3+ through N···H-N hydrogen bonds, form two-dimensional structures. One organic cation, CH3NH3+, that resides in the intralaminar cavity and plays a role as a template, undergoes a temperature-controlled order-disorder structural phase transition. As the frozen-thawed state change of the polar organic cations modifies the polarizability of materials, stepwise dielectric switching is observed at the phase transition temperature. Furthermore, the photo-induced linkage isomerism of [Fe(CN)5NO]2- building block survives in the new compounds at the low-temperature range, which is verified by variable-temperature IR spectra after photo-irradiation. The coexistence of switchable dielectric properties and photo-induced structural variation suggests multiple optical-electric roles of the present materials.
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Many crystalline molecular rotors have been developed in the past decades. However, manipulating the rotational gesture that intrinsically controls the physical performance of materials remains a challenge. Herein, we report a series of crystalline rotors whose rotational gestures can be modulated by modifying the structures of molecular stators. In these dynamic crystals, the ox2- (ox2- = oxalate anion) behave as molecular rotators performing axial-free rotation in cavities composed of five complex cations, [MII(en)3]2+ (en = ethylenediamine). The structure of [MII(en)3]2+ that serves as a molecular stator can be tuned by varying the metal center with different ionic radii, consequently altering the chemical environment around the molecular rotator. Owing to the quasi-transverse isotropy of ox2- and multiple hydrogen-bond interactions around it, the molecular rotator exhibits unusual motional malleability, i.e., it can rotate either longitudinally in the compound of ZnII, or with a tilt angle of 42° in the compound of FeII, or even laterally in the compound of CdII. The atypical dynamic behavior demonstrated here provides a new chance for the development of exquisite crystalline molecular rotors with advanced tunable functionalities.
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Manipulating the collective molecular movements to implement macroscopic mechanical response of bulk material is attractive and challenging. Here, an organic-inorganic hybrid single crystal is synthesized, which exhibits a giant macroscopic shape transformation with a remarkable thermal hysteretic feature. The colossal anisotropic shape change, which manifests as an abrupt elongation of ca. 9 % along the crystallographic c-axis and a concomitant contraction of ca. 9 % in a perpendicular direction, is induced by a significant reorientation of imidazolium, accompanied with a substantial configurational variation in CuBr4 2- complex anions. The synergistic motions of both the molecular cations and anions engender a remarkable large thermal hysteresis (>30â K) in the shape transformation of the single crystal, implying that this material may play a role in alternating memory media. Furthermore, due to the stable crystal lattice, a single crystal that demonstrates naked-eye detectable large shape transformation was used as a thermal actuator to spontaneously control an electric circuit by temperature variation.
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Six analogue compounds with the general formula [Fe2( xL)5(NCS)4]· yMeOH ( x = o-Cl, y = 3 for compound 1; x = m-Cl, y = 5 for 2; x = p-Cl, y = 1 for 3; x = o-Me, y = 2 for 4; x = m-Me, y = 2 for 5; x = p-Me, y = 3 for 6; L = N-phenylmethylene-4-amino-1,2,4-triazole) were synthesized. The two Fe(II) ions are triply bridged by the triazole groups of three xL ligands and each Fe(II) is further capped with two NCS- groups and one more xL ligand. These compounds show regular patterns in their magnetic properties that depend on the positions the substituent groups (-Cl or -Me) ride, i.e., ortho-substituted compounds 1 and 4 undergo complete one-step spin crossover (SCO), while meta-substituted compounds 2 and 5 display incomplete one-step SCO with lower transition temperatures, and para-substituted compounds 3 and 6 are in the high-spin states in all temperature ranges. Structural analyses reveal that the molecular geometry and intermolecular interactions of these compounds, which should account for the differences in magnetic properties, are obviously depend on the positions of substituent groups (steric effect), despite them being electron-withdrawing chlorine or electron-donating methyl, whereas theoretical calculations confirm that the electronic effects of substituent groups exert no effect on the magnetic properties.
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The reaction of 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene (tppe) with [Fe(NCBH3)2] produced a two-dimensional coordination polymer [Fe(NCBH3)2(tppe)]n (1), which was pillared in an ABAB manner through interlayer multiple [C-Hδ+···Hδ--B] dihydrogen bonds (DHBs) to form a stable porous three-dimensional (3D) supramolecular structure that showed guest-molecule-dependent spin-crossover behaviors.
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The grafts of fluorophores 9-anthraldehyde (AD) and 9-phenanthrenecarboxaldehyde (PD), respectively, on the one-dimensional spin-crossover compound [Fe(L)3 ](ClO4 )2 (FeL, L=4-amino-1,2,4-triazole) by post-synthetic aldimine condensation reactions produced two spin-crossover (SCO)-fluorescent hybrid materials, that is, FeL-AD and FeL-PD. The spin-crossover critical temperatures of the two materials both centered at Tc ↓=254 and Tc ↑=256â K, whereas the fluorescence intensities of the two materials featured functions of the temperature that strictly synchronized with the spin-crossover processes, which showed that the ligand-centered fluorescence was dominated by the spin states of the ferrous ions. The bifunctional entities (spin-crossover centers and fluorophores) in FeL-AD or FeL-PD showed spectral band overlap that purported the Förster resonance energy transfer mechanism of such spin-crossover-fluorescence correlation. The post-synthetic modification of SCO materials and the relationship between the fluorescence and the SCO may be helpful in the development of multifunctional materials that can be sensitive to multiple stimuli.
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The development of magnetic molecules with long spin reversal/decoherence times highly depends on the understanding of relaxation behavior under different external conditions. Herein, a magnetic study on a RuIII complex (1) is presented. Detailed analysis of the relaxation time and the magneto-heat capacity data suggests that the resonant phonon trapping process dominates the magnetic relaxation in the crystalline sample of 1, slowing down the spin relaxation rate, as further confirmed by the measurements on a ground sample and frozen solution. Thus, it provides a rare example showing that 4d metal-centered mononuclear compounds without second-order anisotropy can display slow magnetic relaxation.
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An octacoordinated Fe(II) complex, [FeII(dpphen)2](BF4)2·1.3H2O (1; dpphen = 2,9-bis(pyrazol-1-yl)-1,10-phenanthroline), with a pseudo-D2d-symmetric metal center has been synthesized. Magnetic, high-frequency/-field electron paramagnetic resonance (HF-EPR), and theoretical investigations reveal that 1 is characterized by uniaxial magnetic anisotropy with a negative axial zero-field splitting (ZFS) (D ≈ -6.0 cm-1) and a very small rhombic ZFS (E ≈ 0.04 cm-1). Under applied dc magnetic fields, complex 1 exhibits slow magnetic relaxation at low temperature. Fitting the relaxation time with the Arrhenius mode combining Orbach and tunneling terms affords a good fit to all the data and yields an effective energy barrier (17.0 cm-1) close to the energy gap between the ground state and the first excited state. The origin of the strong uniaxial magnetic anisotropy for 1 has been clearly understood from theoretical calculations. Our study suggests that high-coordinated compounds featuring a D2d-symmetric metal center are promising candidates for mononuclear single-molecule magnets.