Metal-Organic Framework Magnets.

Metal-organic frameworks represent the ultimate chemical platform on which to develop a new generation of designer magnets. In contrast to the inorganic solids that have dominated permanent magnet technology for decades, metal-organic frameworks offer numerous advantages, most notably the nearly infinite chemical space through which to synthesize predesigned and tunable structures with controllable properties. Moreover, the presence of a rigid, crystalline structure based on organic linkers enables the potential for permanent porosity and postsynthetic chemical modification of the inorganic and organic components. Despite these attributes, the realization of metal-organic magnets with high ordering temperatures represents a formidable challenge, owing largely to the typically weak magnetic exchange coupling mediated through organic linkers. Nevertheless, recent years have seen a number of exciting advances involving frameworks based on a wide range of metal ions and organic linkers. This review provides a survey of structurally characterized metal-organic frameworks that have been shown to exhibit magnetic order. Section 1 outlines the need for new magnets and the potential role of metal-organic frameworks toward that end, and it briefly introduces the classes of magnets and the experimental methods used to characterize them. Section 2 describes early milestones and key advances in metal-organic magnet research that laid the foundation for structurally characterized metal-organic framework magnets. Sections 3 and 4 then outline the literature of metal-organic framework magnets based on diamagnetic and radical organic linkers, respectively. Finally, Section 5 concludes with some potential strategies for increasing the ordering temperatures of metal-organic framework magnets while maintaining structural integrity and additional function.

Metal-Diamidobenzoquinone Frameworks via Post-Synthetic Linker Exchange.

Metal-organic frameworks with amidic linkers often exhibit exceptional physical properties, but, owing to their strong metal-nitrogen bonds, are exceedingly challenging to isolate through direct synthesis. Here, we report a route to access metal-diamidobenzoquinone frameworks from their dihydroxobenzoquinone counterparts via postsynthetic linker exchange. The parent compounds (Me2NH2)2[M2L3] (M = Zn, Mn; H2L = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone) undergo linker exchange upon exposure to a solution of monodeprotonated 2,5-diamino-3,6-dibromo-1,4-benzoquinone or 2,5-diamino-3,6-dichloro-1,4-benzoquinone, proceeding through single-crystal-to-single-crystal reactions. The presence of both types of linker in the resulting frameworks is confirmed by a combination of NMR, Raman, and energy-dispersive X-ray (EDX) spectroscopies. Moreover, the extent of linker exchange in the Zn frameworks is quantified using 13C NMR spectroscopy, and spatially resolved EDX spectroscopy reveals the two types of linker to be homogeneously distributed within a crystal. Finally, we propose a tentative mechanism of linker exchange based on pKa measurements, considerations of framework solubility, and powder X-ray diffraction analysis. This work provides the first method to exchange organic linkers with different donor atoms in metal-organic frameworks and in doing so demonstrates exchange between linkers with donor atoms differing in acidity by a remarkable 11 units of pKa. Together, these results offer a potentially general synthetic strategy toward new materials with exotic metal-linker coordination modes.

Insensitivity of Magnetic Coupling to Ligand Substitution in a Series of Tetraoxolene Radical-Bridged Fe2 Complexes.

The elucidation of magnetostructural correlations between bridging ligand substitution and strength of magnetic coupling is essential to the development of high-temperature molecule-based magnetic materials. Toward this end, we report the series of tetraoxolene-bridged FeII2 complexes [(Me3TPyA)2Fe2(RL)]n+ (Me3TPyA = tris(6-methyl-2-pyridylmethyl)amine; n = 2: OMeLH2 = 3,6-dimethoxy-2,5-dihydroxo-1,4-benzoquinone, ClLH2 = 3,6-dichloro-2,5-dihydroxo-1,4-benzoquinone, Na2[NO2L] = sodium 3,6-dinitro-2,5-dihydroxo-1,4-benzoquinone; n = 4: SMe2L = 3,6-bis(dimethylsulfonium)-2,5-dihydroxo-1,4-benzoquinone diylide) and their one-electron-reduced analogues. Variable-temperature dc magnetic susceptibility data reveal the presence of weak ferromagnetic superexchange between FeII centers in the oxidized species, with exchange constants of J = +1.2(2) (R = OMe, Cl) and +0.3(1) (R = NO2, SMe2) cm-1. In contrast, X-ray diffraction, cyclic voltammetry, and Mössbauer spectroscopy establish a ligand-centered radical in the reduced complexes. Magnetic measurements for the radical-bridged species reveal the presence of strong antiferromagnetic metal-radical coupling, with J = -57(10), -60(7), -58(6), and -65(8) cm-1 for R = OMe, Cl, NO2, and SMe2, respectively. The minimal effects of substituents in the 3- and 6-positions of RLx-• on the magnetic coupling strength is understood through electronic structure calculations, which show negligible spin density on the substituents and associated C atoms of the ring. Finally, the radical-bridged complexes are single-molecule magnets, with relaxation barriers of Ueff = 50(1), 41(1), 38(1), and 33(1) cm-1 for R = OMe, Cl, NO2, and SMe2, respectively. Taken together, these results provide the first examination of how bridging ligand substitution influences magnetic coupling in semiquinoid-bridged compounds, and they establish design criteria for the synthesis of semiquinoid-based molecules and materials.

Selective Binding and Quantitation of Calcium with a Cobalt-Based Magnetic Resonance Probe.

We report a cobalt-based paramagnetic chemical exchange saturation transfer (PARACEST) magnetic resonance (MR) probe that is able to selectively bind and quantitate the concentration of Ca2+ ions under physiological conditions. The parent LCo complex features CEST-active carboxamide groups and an uncoordinated crown ether moiety in close proximity to a high-spin pseudo-octahedral CoII center. Addition of Na+, Mg2+, K+, and Ca2+ leads to binding of these metal ions within the crown ether. Single-crystal X-ray diffraction and solid-state magnetic measurements reveal the presence of a cation-specific coordination environment and magnetic anisotropy of CoII, with axial zero-field splitting parameters for the Na+- and Ca2+-bound complexes differing by over 90%. Owing to these differences, solution-based measurements under physiological conditions indicate reversible binding of Na+ and Ca2+ to give well-separated CEST peaks at 69 and 80 ppm for [LCoNa]+ and [LCoCa]2+, respectively. Dissociation constants for different cation-bound complexes of LCo, as determined by 1H NMR spectroscopy, demonstrate high selectivity toward Ca2+. This finding, in conjunction with the large excess of Na+ in physiological environments, minimizes interference from related cations, such as Mg2+ and K+. Finally, variable-[Ca2+] CEST spectra establish the ratio between the CEST peak intensities for the Ca2+- and Na+-bound probes (CEST80 ppm/CEST69 ppm) as a measure of [Ca2+], providing the first example of a ratiometric quantitation of Ca2+ concentration using PARACEST. Taken together, these results demonstrate the ability of transition metal PARACEST probes to afford a concentration-independent measure of [Ca2+] and provide a new approach for designing MR probes for cation sensing.

A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State.

Structural and spectroscopic characterization of the dimeric iron hydride complex [Ph2B(tBuIm)2FeH]2 reveals an unusual structure in which a tetrahedral iron(II) site (S = 2) is connected to a square planar iron(II) site (S = 1) by two bridging hydride ligands. Magnetic susceptibility reveals strong ferromagnetic coupling between iron centers, with a coupling constant of J = +110(12) cm-1, to give an S = 3 ground state. High-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy confirms this model. A qualitative molecular orbital analysis of the electronic structure, as supported by electronic structure calculations, reveals that the observed spin configuration results from the orthogonal alignment of two geometrically distinct four-coordinate iron fragments held together by highly covalent hydride ligands.

Strong π-Backbonding Enables Record Magnetic Exchange Coupling Through Cyanide.

The paramagnetic cyano-bridged complex PhB(tBuIm)3Fe-NC-Mo(NtBuAr)3 (Ar = 3,5-Me2C6H3) is readily assembled from a new four-coordinate, high-spin (S = 2) iron(II) monocyanide complex and the three-coordinate molybdenum(III) complex Mo(NtBuAr)3. X-ray diffraction and IR spectroscopy reveal that delocalization of unpaired electron density into the cyanide π* orbitals leads to a reduction of the C-N bond order. Direct current (dc) magnetic susceptibility measurements, supported by electronic structure calculations, demonstrate the presence of strong antiferromagnetic exchange between spin centers, with a coupling constant of J = -122(2) cm-1. To our knowledge, this value represents the strongest magnetic exchange coupling ever to be observed through cyanide. These results demonstrate the ability of low-coordinate metal fragments to engender extremely strong magnetic exchange coupling through cyanide by virtue of significant π-backbonding into the cyanide ligand.

Thiosemiquinoid Radical-Bridged CrIII2 Complexes with Strong Magnetic Exchange Coupling.

Semiquinoid radical bridging ligands are capable of mediating exceptionally strong magnetic coupling between spin centers, a requirement for the design of high-temperature magnetic materials. We demonstrate the ability of sulfur donors to provide much stronger coupling relative to their oxygen congeners in a series of dinuclear complexes. Employing a series of chalcogen donor-based bis(bidentate) benzoquinoid bridging ligands, the series of complexes [(TPyA)2Cr2(RL4-)]2+ (OLH4 = 1,2,4,5-tetrahydroxybenzene, OSLH4 = 1,2-dithio-4,5-dihydroxybenzene, SLH4 = 1,2,4,5-tetrathiobenzene, TPyA = tris(2-pyridylmethyl)amine) was synthesized. Variable-temperature dc magnetic susceptibility data reveal the presence of weak antiferromagnetic superexchange coupling between CrIII centers in these complexes, with exchange constants of J = -2.83(3) (OL4-), -2.28(5) (OSL4-), and -1.80(2) (SL4-) cm-1. Guided by cyclic voltammetry and spectroelectrochemical measurements, chemical one-electron oxidation of these complexes gives the radical-bridged species [(TPyA)2Cr2(RL3-•)]3+. Variable-temperature dc susceptibility measurements in these complexes reveal the presence of strong antiferromagnetic metal-semiquinoid radical coupling, with exchange constants of J = -352(10) (OL3-•), - 401(8) (OSL3-•), and -487(8) (SL3-•) cm-1. These results provide the first measurement of magnetic coupling between metal ions and a thiosemiquinoid radical, and they demonstrate the value of moving from O to S donors in radical-bridged metal ions in the design of magnetic molecules and materials.

A Ferric Semiquinoid Single-Chain Magnet via Thermally-Switchable Metal-Ligand Electron Transfer.

We report the synthesis of a semiquinoid-bridged single-chain magnet, as generated through a thermally induced metal-ligand electron transfer. Reaction of FeCl3 with 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (LH2) in the presence of (NMe4)Cl gave the compound (NMe4)2[LFeCl2]. Together, variable-temperature X-ray diffraction, Mössbauer spectra, Raman spectra, and dc magnetic susceptibility reveal a transition from a chain containing (L2-)FeII units to one with (L3-•)FeIII upon decreasing temperature, with a transition temperature of T1/2 = 213 K. The dc magnetic susceptibility measurements show strong metal-radical coupling within the chain, with a coupling constant of J = -81 cm-1, and ac susceptibility data reveal slow magnetic relaxation, with a relaxation barrier of Δτ = 55(1) cm-1. To our knowledge, this compound provides the first example of a semiquinoid-bridged single-chain magnet.

Harnessing Structural Dynamics in a 2D Manganese-Benzoquinoid Framework To Dramatically Accelerate Metal Transport in Diffusion-Limited Metal Exchange Reactions.

Postsynthetic metal exchange represents a powerful synthetic method to generate metal-organic frameworks (MOFs) that are not accessible through direct synthesis, yet it is often hampered by slow reaction kinetics and incomplete exchange. While studies of metal exchange reactions have primarily focused on the transmetalation process, transport of exogenous metal ions into the framework structure represents a critical yet underexplored process. Here, we employ X-ray crystallography, electron microscopy, and energy dispersive X-ray spectroscopy to comprehensively examine the transport of Co2+ and Zn2+ ions during postsynthetic metal exchange reactions within the 2D manganese-benzoquinoid framework (Et4N)2[Mn2L3] (H2L = 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone). These studies reveal that exogenous metal ions diffuse primarily through the 1D channel along the crystallographic c axis, and this transport represents the rate-determining step. In addition, the Mn framework exhibits reversible dynamic structure behavior, contracting upon desolvation and then rapidly restoring its original structure and full volume upon resolvation. When conducting metal exchange reactions using a partially desolvated sample, these structural dynamics lead to acceleration of metal transport by up to 2000-fold, improve product purity, and give exchange of a larger fraction of metal sites. Finally, upon performing metal exchange using full-solvated crystals, an intermediate product can be isolated that constitutes a unique example of a 2D material with a gradient vertical heterostructure.

Electronic Effects of Ligand Substitution in a Family of CoII2 PARACEST pH Probes.

We report three new Co2-based paramagnetic chemical exchange saturation transfer (PARACEST) probes with the ability to ratiometrically quantitate pH. A CoII2 complex, [LCo2(etidronate)]-, featuring tetra(carboxamide) and OH-substituted etidronate ligands with opposing pH-dependent CEST peak intensities, was previously shown to exhibit a linear correlation between log(CESTOH/CESTNH) and pH in the pH range 6.5-7.6 that provided a sensitivity of 0.99(7) pH unit-1 at 37 °C. Here, we demonstrate through a series of CF3-functionalized CoII2 complexes [(XL')Co2(etidronate)]- (X = NO2, F, Me), that modest changes in the electronic structure of CoII centers through remote ligand substitution can significantly affect the NMR and CEST properties of Co2-based PARACEST probes. Variable-pH NMR and CEST analyses reveal that the chemical shifts of the ligand protons are highly affected by the nature of the X substituent. The ratios of OH and NH CEST peak intensities at 115 and 88, 93 and 79, and 88 and 76 ppm for X = NO2, F, and Me, respectively, afford pH calibration curves with remarkably high sensitivities of 1.49(9), 1.48(7), and 2.04(5) pH unit-1 across the series. The 1.5-2-fold enhancement in pH sensitivity for the CF3-functionalized Co2 probes stems from the complete separation of the OH and NH CEST peaks. Furthermore, incorporation of electron-withdrawing CF3 groups shifts the detection window to a more acidic range of pH 6.2-7.4. Finally, the CoII2 complexes are found to be extremely robust toward substitution and oxidation in aqueous solutions. Taken together, these results highlight the unique ability of transition metal-based PARACEST probes to provide a highly sensitive concentration-independent measure of pH and demonstrate that modest ligand modifications can be a powerful tool for optimizing the pH sensing performance of these probes.

Effect of Magnetic Coupling on Water Proton Relaxivity in a Series of Transition Metal GdIII Complexes.

A fundamental challenge in the design of bioresponsive (or bioactivated) GdIII-based magnetic resonance (MR) imaging probes is the considerable background signal present in the "preactivated" state that arises from outer-sphere relaxation processes. When sufficient concentrations of a bioresponsive agent are present (i.e., a detectable signal in the image), the inner- and outer-sphere contributions to r1 may be misinterpreted to conclude that the agent has been activated, when it has not. Of the several parameters that determine the observed MR signal of an agent, only the electron relaxation time ( T1e) impacts both the inner- and outer-sphere relaxation. Therefore, strategies to minimize this background signal must be developed to create a near zero-background (or truly "off" state) of the agent. Here, we demonstrate that intramolecular magnetic exchange coupling when GdIII is coupled to a paramagnetic transition metal provides a means to overcome the contribution of second- and outer-sphere contributions to the observed relaxivity. We have prepared a series of complexes with the general formula LMLn(µ-O2CCH3)(O2CCH3)2 (M = Co, Cu, Zn). Solid-state magnetic susceptibility measurements reveal significant magnetic coupling between GdIII and the transition metal ion. Nuclear magnetic relaxation dispersion (NMRD) analysis confirms that the observed differences in relaxivity are associated with the modulation of T1e at GdIII. These results clearly demonstrate that magnetic exchange coupling between GdIII and a transition metal ion can provide a significant decrease in T1e (and therefore the relaxivity of GdIII). This design strategy is being exploited to prepare new generations of preclinical bioresponsive MR imaging probes with near zero-background.

2D Conductive Iron-Quinoid Magnets Ordering up to Tc = 105 K via Heterogenous Redox Chemistry.

We report the magnetism and conductivity for a redox pair of iron-quinoid metal-organic frameworks (MOFs). The oxidized compound, (Me2NH2)2[Fe2L3]·2H2O·6DMF (LH2 = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone) was previously shown to magnetically order below 80 K in its solvated form, with the ordering temperature decreasing to 26 K upon desolvation. Here, we demonstrate this compound to exhibit electrical conductivity values up to σ = 1.4(7) × 10-2 S/cm (Ea = 0.26(1) cm-1) and 1.0(3) × 10-3 S/cm (Ea = 0.19(1) cm-1) in its solvated and desolvated forms, respectively. Upon soaking in a DMF solution of Cp2Co, the compound undergoes a single-crystal-to-single-crystal one-electron reduction to give (Cp2Co)1.43(Me2NH2)1.57[Fe2L3]·4.9DMF. Structural and spectroscopic analysis confirms this reduction to be ligand-based, and as such the trianionic framework is formulated as [FeIII2(L3-•)3]3-. Magnetic measurements for this reduced compound reveal the presence of dominant intralayer metal-organic radical coupling to give a magnetically ordered phase below Tc = 105 K, one of the highest reported ordering temperatures for a MOF. This high ordering temperature is significantly increased relative to the oxidized compound, and stems from the overall increase in coupling strength afforded by an additional organic radical. In line with the high critical temperature, the new MOF exhibits magnetic hysteresis up to 100 K, as revealed by variable-field measurements. Finally, this compound is electrically conductive, with values up to σ = 5.1(3) × 10-4 S/cm with Ea = 0.34(1) eV. Taken together, these results demonstrate the unique ability of metal-quinoid MOFs to simultaneously exhibit both high magnetic ordering temperatures and high electrical conductivity.

A Porous Array of Clock Qubits.

Realizing atomic-level spatial control over qubits, the fundamental units of both quantum information processing systems and quantum sensors, constitutes a crucial cross-field challenge. Toward this end, embedding electronic-spin-based qubits within the framework of a crystalline porous material is a promising approach to create precise arrays of qubits. Realizing porous hosts for qubits would also impact the emerging field of quantum sensing, whereby porosity would enable analytes to infuse into a sensor matrix. However, building viable qubits into a porous material is an appreciable challenge because of the extreme sensitivity of qubits to local magnetic noise. To insulate these frameworks from ambient magnetic signals, we borrowed from atomic physics the idea to exploit clock transitions at avoided level crossings. Here, sensitivity to magnetic noise is inherently limited by the flat slope of the so-called clock transition. More specifically, we created an array of clocklike qubits within a metal-organic framework by combining coordination chemistry considerations with the fundamental concept of atomic clock transitions. Electron paramagnetic resonance studies verify a clocklike transition for the hosted cobalt(II) spins in the framework [(TCPP)Co0.07Zn0.93]3[Zr6O4(OH)4(H2O)6]2, the first demonstration in any porous material. The clocklike qubits display lifetimes of up to 14 µs despite abundant local nuclear spins, illuminating a new path toward proof-of-concept quantum sensors and processors with high inherent structural precision.

Ratiometric pH Imaging with a CoII2 MRI Probe via CEST Effects of Opposing pH Dependences.

We report a Co2-based magnetic resonance (MR) probe that enables the ratiometric quantitation and imaging of pH through chemical exchange saturation transfer (CEST). This approach is illustrated in a series of air- and water-stable CoII2 complexes featuring CEST-active tetra(carboxamide) and/or hydroxyl-substituted bisphosphonate ligands. For the complex bearing both ligands, variable-pH CEST and NMR analyses reveal highly shifted carboxamide and hydroxyl peaks with intensities that increase and decrease with increasing pH, respectively. The ratios of CEST peak intensities at 104 and 64 ppm are correlated with solution pH in the physiological range 6.5-7.6 to construct a linear calibration curve of log(CEST104 ppm/CEST64 ppm) versus pH, which exhibits a remarkably high pH sensitivity of 0.99(7) pH unit-1 at 37 °C. In contrast, the analogous CoII2 complex with a CEST-inactive bisphosphonate ligand exhibits no such pH response, confirming that the pH sensitivity stems from the integration of amide and hydroxyl CEST effects that show base- and acid-catalyzed proton exchange, respectively. Importantly, the pH calibration curve is independent of the probe concentration and is identical in aqueous buffer and fetal bovine serum. Furthermore, phantom images reveal analogous linear pH behavior. The CoII2 probe is stable toward millimolar concentrations of H2PO4-/HPO42-, CO32-, SO42-, CH3COO-, and Ca2+ ions, and more than 50% of melanoma cells remain viable in the presence of millimolar concentrations of the complex. The stability of the probe in physiological environments suggests that it may be suitable for in vivo studies. Together, these results highlight the ability of dinuclear transition metal PARACEST probes to provide a concentration-independent measure of pH, and they provide a potential design strategy toward the development of MR probes for ratiometric pH imaging.

CO Binding at a Four-Coordinate Cobaltous Porphyrin Site in a Metal-Organic Framework: Structural, EPR, and Gas Adsorption Analysis.

The variable-temperature CO binding at a four-coordinate cobaltous porphyrin complex within a metal-organic framework is investigated using a combined array of infrared, X-ray diffraction, EPR, and CO adsorption analysis. Single-crystal X-ray diffraction experiments provide the first crystallographically characterized example of a noniron first-row transition metal porphyrin carbonyl adduct. Variable-temperature electron paramagnetic resonance spectroscopy supports the structural observation and reveals conversion of the dicarbonyl complex to a monocarbonyl species as temperature is increased. Finally, CO adsorption analysis data enable quantification of the Co-CO interaction, providing a binding enthalpy of hads = -29(2) kJ/mol. This value is nearly twice that observed for O2 binding in the same compound and is attributed to a stronger σ interaction for Co and CO vs O2. These results demonstrate the ability of MOFs to enable a thorough investigation of CO binding in metalloporphyrins.

Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes.

High-oxidation-state metal complexes with multiply bonded ligands are of great interest for both their reactivity as well as their fundamental bonding properties. This paper reports a combined spectroscopic and theoretical investigation into the effect of the apical multiply bonded ligand on the spin-state preferences of threefold symmetric iron(IV) complexes with tris(carbene) donor ligands. Specifically, singlet (S = 0) nitrido [{PhB(ImR)3}FeN], R = tBu (1), Mes (mesityl, 2) and the related triplet (S = 1) imido complexes, [{PhB(ImR)3}Fe(NR')]+, R = Mes, R' = 1-adamantyl (3), tBu (4), were investigated by electronic absorption and Mössbauer effect spectroscopies. For comparison, two other Fe(IV) nitrido complexes, [(TIMENAr)FeN]+ (TIMENAr = tris[2-(3-aryl-imidazol-2-ylidene)ethyl]amine; Ar = Xyl (xylyl), Mes), were investigated by 57Fe Mössbauer spectroscopy, including applied-field measurements. The paramagnetic imido complexes 3 and 4 were also studied by magnetic susceptibility measurements (for 3) and paramagnetic resonance spectroscopy: high-frequency and -field electron paramagnetic resonance (for 3 and 4) and frequency-domain Fourier-transform (FD-FT) terahertz electron paramagnetic resonance (for 3), which reveal their zero-field splitting parameters. Experimentally correlated theoretical studies comprising ligand-field theory and quantum chemical theory, the latter including both density functional theory and ab initio methods, reveal the key role played by the Fe 3dz2 (a1) orbital in these systems: the nature of its interaction with the nitrido or imido ligand dictates the spin-state preference of the complex. The ability to tune the spin state through the energy and nature of a single orbital has general relevance to the factors controlling spin states in complexes with applicability as single molecule devices.

A Cu(II)2 Paramagnetic Chemical Exchange Saturation Transfer Contrast Agent Enabled by Magnetic Exchange Coupling.

The ability of magnetic exchange coupling to enable observation of paramagnetic chemical exchange saturation transfer (PARACEST) in transition metal ions with long electronic relaxation times (τs) is demonstrated. Metalation of the dinucleating, tetra(carboxamide) ligand HL with Cu(2+) in the presence of pyrophosphate (P2O7)(4-) affords the complex [LCu(II)2(P2O7)](-). Solution-phase variable-temperature magnetic susceptibility data reveal weak ferromagnetic superexchange coupling between the two S = 1/2 Cu(II) centers, with a coupling constant of J = +2.69(5) cm(-1), to give an S = 1 ground state. This coupling results in a sharpened NMR line width relative to a GaCu analogue, indicative of a shortening of τs. Presaturation of the amide protons in the Cu2 complex at 37 °C leads to a 14% intensity decrease in the bulk water (1)H NMR signal through the CEST effect. Conversely, no CEST effect is observed in the GaCu complex. These results provide the first example of a Cu-based PARACEST magnetic resonance contrast agent and demonstrate the potential to expand the metal ion toolbox for PARACEST agents through introduction of magnetic exchange coupling.

Solid-State Redox Switching of Magnetic Exchange and Electronic Conductivity in a Benzoquinoid-Bridged Mn(II) Chain Compound.

We demonstrate that incorporation of a redox-active benzoquinoid ligand into a one-dimensional chain compound can give rise to a material that exhibits simultaneous solid-state redox switching of optical, magnetic, and electronic properties. Metalation of the ligand 4,5-bis(pyridine-2-carboxamido)-1,2-catechol ((N,O)LH4) with Mn(III) affords the chain compound Mn((N,O)L)(DMSO). Structural and spectroscopic analysis of this compound show the presence of Mn(II) centers bridged by (N,O)L(2-) ligands, resulting partially from a spontaneous ligand-to-metal electron transfer. Upon soaking in a solution of the reductant Cp2Co, Mn((N,O)L)(DMSO) undergoes a ligand-centered solid-state reduction to [Mn((N,O)L)](-), as revealed by a suite of techniques, including Raman and X-ray absorption spectroscopy. The ligand-based reduction engenders a dramatic modulation of the physical properties of the chain compound. An electrochromic response, evidenced by a color change from dark green to dark purple is accompanied by a nearly 40-fold increase in magnetic coupling strength, from J = -0.38(1) to -15.6(2) cm(-1), and a 10,000-fold increase in electronic conductivity, from σ = 2.33(1) × 10(-12) S/cm (Ea = 0.64(1) eV) to 8.61(1) × 10(-8) S/cm (Ea = 0.39(1) eV). Importantly, the chemical reduction is reversible: treatment of the reduced compound with [Cp2Fe](+) regenerates the oxidized chain. Taken together, these results highlight the ability of benzoquinoid ligands to facilitate solid-state ligand-based redox reactions in nonporous coordination solids, giving rise to reversible switching of optical properties, magnetic exchange interactions, and electronic conductivity.

A 2D Semiquinone Radical-Containing Microporous Magnet with Solvent-Induced Switching from Tc = 26 to 80 K.

The incorporation of tetraoxolene radical bridging ligands into a microporous magnetic solid is demonstrated. Metalation of the redox-active bridging ligand 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (LH2) with Fe(II) affords the solid (Me2NH2)2[Fe2L3]·2H2O·6DMF. Analysis of X-ray diffraction, Raman spectra, and Mössbauer spectra confirm the presence of Fe(III) centers with mixed-valence ligands of the form (L3)(8-) that result from a spontaneous electron transfer from Fe(II) to L(2-). Upon removal of DMF and H2O solvent molecules, the compound undergoes a slight structural distortion to give the desolvated phase (Me2NH2)2[Fe2L3], and a fit to N2 adsorption data of this activated compound gives a BET surface area of 885(105) m(2)/g. Dc magnetic susceptibility measurements reveal a spontaneous magnetization below 80 and 26 K for the solvated and the activated solids, respectively, with magnetic hysteresis up to 60 and 20 K. These results highlight the ability of redox-active tetraoxolene ligands to support the formation of a microporous magnet and provide the first example of a structurally characterized extended solid that contains tetraoxolene radical ligands.

Electron Hopping through Double-Exchange Coupling in a Mixed-Valence Diiminobenzoquinone-Bridged Fe2 Complex.

The ability of a benzoquinonoid bridging ligand to mediate double-exchange coupling in a mixed-valence Fe2 complex is demonstrated. Metalation of the bridging ligand 2,5-di(2,6-dimethylanilino)-3,6-dibromo-1,4-benzoquinone (LH2) with Fe(II) in the presence of the capping ligand tris((6-methyl-2-pyridyl)methyl)amine (Me3TPyA) affords the dinuclear complex [(Me3TPyA)2Fe(II)2(L)](2+). The dc magnetic measurements, in conjunction with X-ray diffraction and Mössbauer spectroscopy, reveal the presence of weak ferromagnetic superexchange coupling between Fe(II) centers through the diamagnetic bridging ligand to give an S = 4 ground state. The ac magnetic susceptibility measurements, collected in a small dc field, show this complex to behave as a single-molecule magnet with a relaxation barrier of U(eff) = 14(1) cm(-1). The slow magnetic relaxation in the Fe(II)2 complex can be switched off through one-electron oxidation to the mixed-valence congener [(Me3TPyA)2Fe2(L)](3+), where X-ray diffraction and Mössbauer spectroscopy indicate a metal-centered oxidation. The dc magnetic measurements show an S = 9/2 ground state for the mixed-valence complex, stemming from strong ferromagnetic exchange coupling that is best described considering electron hopping through a double-exchange coupling mechanism, with a double-exchange parameter of B = 69(4) cm(-1). In accordance with double-exchange, an intense feature is observed in the near-infrared region and is assigned as an intervalence charge-transfer band. The rate of intervalence electron hopping is comparable to that of the Mössbauer time scale, such that variable-temperature Mössbauer spectra reveal a thermally activated transition from a valence-trapped to detrapped state and provide an activation energy for electron hopping of 63(8) cm(-1). These results demonstrate the ability of quinonoid ligands to mediate electron hopping between high-spin metal centers, by providing the first example of an Fe complex that exhibits double-exchange through an organic bridging ligand and the largest metal-metal separation yet observed in any metal complex with double-exchange coupling.