Kinetic control of interpenetration in Fe-biphenyl-4,4′-dicarboxylate metal-organic frameworks by coordination and oxidation modulation

Phase control in the self-assembly of metal-organic frameworks (MOFs) is often a case of trial and error; judicious control over a number of synthetic variables is required to select the desired topology and control features such as interpenetration and defectivity. Herein, we present a comprehensive investigation of self-assembly in the Fe-biphenyl-4,4′-dicarboxylate system, demonstrating that coordination modulation can reliably tune between the kinetic product, non-interpenetrated MIL-88D(Fe), and the thermodynamic product, two-fold interpenetrated MIL-126(Fe). Density functional theory simulations reveal that correlated disorder of the terminal anions on the metal clusters results in hydrogen-bonding between adjacent nets in the interpenetrated phase and is the thermodynamic driving force for its formation. Coordination modulation slows self-assembly and therefore selects the thermodynamic product MIL-126(Fe), while offering fine control over defectivity, inducing mesoporosity, but electron microscopy shows MIL-88D(Fe) persists in many samples despite not being evident by diffraction. Interpenetration control is also demonstrated using the 2,2′-bipyridine-5,5′-dicarboxylate linker; it is energetically prohibitive for it to adopt the twisted conformation required to form the interpenetrated phase, although multiple alternative phases are identified due to additional coordination of Fe cations to its N-donors. Finally, we introduce oxidation modulation – the use of metal precursors in different oxidation states to that found in the final MOF – to kinetically control self-assembly. Combining coordination and oxidation modulation allows the synthesis of pristine MIL-126(Fe) with BET surface areas close to the predicted maximum for the first time, suggesting that combining the two may be a powerful methodology for the controlled self-assembly of high-valent MOFs

Bidirectional photoswitching of magnetic properties at room temperature: ligand-driven light-induced valence tautomerism

Valence tautomeric (VT) metal complexes are highly promising bistable molecular compounds for applications as molecular switches in molecular electronics and spintronics. Although VT species can be switched with light, the photoswitching in all reported systems requires very low temperatures (usually below 20 K) because photoinduced states are highly unstable at room temperature. The thermal instability hinders any practical application of these complexes in genuine devices. In this report, for the first time we demonstrate photoswitching of VT species and associated magnetic properties at room temperature. The bidirectional photoswitching in solution is due to cis–trans photoisomerizable 4-styrylpyridine ligands deliberately integrated into cobalt dioxolene molecular complexes. The novel type of photoswitching has been coined Ligand-Driven Light-Induced Valence Tautomerism (LD-LIVT). The photoconversion of VT states of 28% has been achieved in solution at room temperature. The photoinduced states show extraordinary thermal stability for hours at room temperature, as compared to common nanoseconds reported previously. The switching proceeds at molecular level with the effective photoswitching rate of 3 × 1013 molecules per s under our conditions. Consequently, this work may open new horizons in applications of molecular switches based on VT metal complexes in molecular devices functioning at room temperature

Reversible Shifting of a Chemical Equilibrium by Light: The Case of Keto-Enol Tautomerism of a β-Ketoester

Manipulating the equilibrium between a ketone and an enol by exposure to light opens up ample opportunities in material chemistry and photopharmacology since it allows one to reversibly control the content of the enol tautomer, which acts as a hydrogen atom donor, with high spatio-temporal and energy resolution. Although tautomerization of β-ketoesters or their analogs was studied in numerous papers, their light-induced reversible tautomerization to give thermally stable enols (photoenolization) is an unexplored area. To shed light on this “blind spot”, we report an unprecedented property of diarylethene 2A assembled from fragments of photoactive dithienylethene and a β-ketoester as part of the cyclohexenone bridge. In a pristine state, the tautomeric equilibrium of 2 is almost completely shifted towards the ketone. Photocyclization of the hexatriene system results in a new equilibrium system containing a significant fraction of the enol tautomer, both in polar and non-polar solvents. Due to the considerable spectral separation (35 nm), the keto-enol tautomerization process could be observed visually. The tendency of 2A to undergo light-induced enolization was proved by isolating a related byproduct of photochemical 1,2-dyotropic rearrangement stabilized in the enolic form. Our results provide a novel tool for controlling the keto-enol tautomerism that might find use in the development of novel photocontrollable processes

Spin Crossover Meets Diarylethenes: Efficient Photoswitching of Magnetic Properties in Solution at Room Temperature

A photoisomerizable diarylethene-derived ligand, phen*, has been successfully introduced into a spin-crossover iron­(II) complex, [Fe­(H₂B­(pz)₂)₂phen*] (<b>1</b>; pz =1-pyrazolyl). A ligand-based photocyclization (photocycloreversion) in <b>1</b> modifies the ligand field, which, in turn, results in a highly efficient paramagnetic high-spin → diamagnetic low-spin (low-spin → high-spin) transition at the coordinated Fe^II ion. The reversible photoswitching of the spin states, and thus the associated magnetic properties, has been performed in solution at room temperature and has been directly monitored by measuring the magnetic susceptibility via the Evans method. The observed spin-state photoconversion in <b>1</b> exceeds 40%, which is the highest value for spin-crossover molecular switches in solution at room temperature reported to date. The photoexcited state is extraordinarily thermally stable, showing a half-time of about 18 days in solution at room temperature. Because of the outstanding photophysical properties of diarylethenes, including single-crystalline photochromism, molecular switch <b>1</b> may offer a promising platform for controlling the magnetic properties in the solid state and ultimately at the single-molecule level with light at room temperature

Spin Crossover Meets Diarylethenes: Efficient Photoswitching of Magnetic Properties in Solution at Room Temperature

A photoisomerizable diarylethene-derived ligand, phen*, has been successfully introduced into a spin-crossover iron­(II) complex, [Fe­(H₂B­(pz)₂)₂phen*] (<b>1</b>; pz =1-pyrazolyl). A ligand-based photocyclization (photocycloreversion) in <b>1</b> modifies the ligand field, which, in turn, results in a highly efficient paramagnetic high-spin → diamagnetic low-spin (low-spin → high-spin) transition at the coordinated Fe^II ion. The reversible photoswitching of the spin states, and thus the associated magnetic properties, has been performed in solution at room temperature and has been directly monitored by measuring the magnetic susceptibility via the Evans method. The observed spin-state photoconversion in <b>1</b> exceeds 40%, which is the highest value for spin-crossover molecular switches in solution at room temperature reported to date. The photoexcited state is extraordinarily thermally stable, showing a half-time of about 18 days in solution at room temperature. Because of the outstanding photophysical properties of diarylethenes, including single-crystalline photochromism, molecular switch <b>1</b> may offer a promising platform for controlling the magnetic properties in the solid state and ultimately at the single-molecule level with light at room temperature

Kinetic Control of Interpenetration in Fe-Biphenyl-4,4′-dicarboxylate MOFs by Coordination and Oxidation Modulation

Phase control in the self-assembly of metal-organic frameworks (MOFs) – materials wherein organic ligands connect metal ions or clusters into network solids with potential porosity – is often a case of trial and error. Judicious control over a number of synthetic variables is required to select for the desired topology and control features such as interpenetration and defectivity, which have significant impact on physical properties and application. Herein, we present a comprehensive investigation of self-assembly in the Fe-biphenyl-4,4\u27-dicarboxylate system, demonstrating that coordination modulation, the addition of competing ligands into solvothermal syntheses, can reliably tune between the kinetic product, non-interpenetrated MIL-88D(Fe), and the thermodynamic product, two-fold interpenetrated MIL-126(Fe). DFT simulations reveal that correlated disorder of the terminal anions on the metal clusters in the interpentrated phase results in H-bonding between adjacent nets and is the thermodynamic driving force for its formation. Coordination modulation slows self-assembly and therefore selects the thermodynamic product MIL-126(Fe), while offering fine control over defectivity, inducing mesoporosity, but electron microscopy shows the MIL-88D(Fe) phase persists in many samples despite not being evident in diffraction experiments, suggesting its presence accounts for the lower than predicted surface areas reported for samples to date. Interpenetration control is also demonstrated by utilizing the 2,2\u27-bipyridine-5,5\u27-dicarboxylate linker; DFT simulations show that it is energetically prohibitive for it to adopt the twisted conformation required to form the interpenetrated phase, and are confirmed by experimental data, although multiple alternative phases are identified due to additional coordination of the Fe cations to the N-donors of the ligand. Finally, we introduce oxidation modulation – the concept of using metal precursors in a different oxidation state to that found in the final MOF – as a further protocol to kinetically control self-assembly. Combining coordination and oxidation modulation allows the synthesis of pristine MIL-126(Fe) with BET surface areas close to the predicted maximum capacity for the first time, suggesting that combining the two may be a powerful methodology for the controlled self-assembly of high-valent MOFs.<br /

Cooperative reduction by Ln2+ and Cp*− ions: synthesis and properties of Sm, Eu, and Yb complexes with 3,6-di-tert-butyl-o-benzoquinone

The first examples of samarium, europium, and ytterbium complexes with 3,6-di-tert-butyl-o-benzoquinone (3,6-dbbq) in the form of catecholate have been obtained by reactions of the quinone with the corresponding lanthanocenes, Image ID:c5dt03573b-t2.gif (n = 1 or 2) in solution. In the course of the reactions lanthanide ions lose one or two Cp* ligands, which take part in reduction of a quinone molecule into a catecholate anion (dbcat, 2−). As a result of the reactions, Sm and Yb clearly yield dimeric complexes [(LnCp*)2(dbcat)2], where each Ln ion loses one Cp* ligand. Eu forms a trimeric complex [(EuCp*)(Eu·thf)2(dbcat)3], in which one Eu ion is coordinated by one Cp* ligand, while two Eu ions have lost all Cp* ligands and are coordinated by THF molecules instead. Magnetic properties corroborate the assignment of oxidation states made on the basis of single-crystal X-ray diffraction: all the quinone ligands are present in the catecholate state; both Sm/Yb ions in the dimers are in the +3 oxidation state, whereas the Eu trimer contains two Eu(II) and one Eu(III) ions. Cyclovoltammetry studies show the presence of two reversible oxidation waves for all complexes, presumably concerned with the redox transitions of the dbcat ligands

Unraveling the electronic structures of low-valent naphthalene and anthracene iron complexes: x-ray, spectroscopic, and density functional theory studies

Naphthalene and anthracene transition metalates are potent reagents, but their electronic structures have remained poorly explored. A study of four Cp*-substituted iron complexes (Cp* = pentamethylcyclopentadienyl) now gives rare insight into the bonding features of such species. The highly oxygen- and water-sensitive compounds [K(18-crown- 6){Cp*Fe(η4-C10H8)}] (K1), [K(18-crown-6){Cp*Fe(η4-C14H10)}] (K2), [Cp*Fe(η4-C10H8)] (1), and [Cp*Fe(η4-C14H10)] (2) were synthesized and characterized by NMR, UV−vis, and 57Fe Mössbauer spectroscopy. The paramagnetic complexes 1 and 2 were additionally characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility measurements. The molecular structures of complexes K1, K2, and 2 were determined by single-crystal X-ray crystallography. Cyclic voltammetry of 1 and 2 and spectroelectrochemical experiments revealed the redox properties of these complexes, which are reversibly reduced to the monoanions [Cp*Fe(η4-C10H8)]− (1−) and [Cp*Fe(η4-C14H10)]− (2−) and reversibly oxidized to the cations [Cp*Fe(η6-C10H8)]+ (1+) and [Cp*Fe(η6-C14H10)]+ (2+). Reduced orbital charges and spin densities of the naphthalene complexes 1−/0/+ and the anthracene derivatives 2−/0/+ were obtained by density functional theory (DFT) methods. Analysis of these data suggests that the electronic structures of the anions 1− and 2− are best represented by low-spin FeII ions coordinated by anionic Cp* and dianionic naphthalene and anthracene ligands. The electronic structures of the neutral complexes 1 and 2 may be described by a superposition of two resonance configurations which, on the one hand, involve a low-spin FeI ion coordinated by the neutral naphthalene or anthracene ligand L, and, on the other hand, a low-spin FeII ion coordinated to a ligand radical L•−. Our study thus reveals the redox noninnocent character of the naphthalene and anthracene ligands, which effectively stabilize the iron atoms in a low formal, but significantly higher spectroscopic oxidation state

Tuning Spin–Spin Coupling in Quinonoid-Bridged Dicopper(II) Complexes through Rational Bridge Variation

Bridged metal complexes [{Cu­(tmpa)}₂­(μ-L¹_–2H)]­(ClO₄)₂ (<b>1</b>), [{Cu­(tmpa)}₂­(μ-L²_–2H)]­(ClO₄)₂ (<b>2</b>), [{Cu­(tmpa)}₂­(μ-L³_–2H)]­(BPh₄)₂ (<b>3</b>), and [{Cu­(tmpa)}₂­(μ-L⁴_–2H)]­(ClO₄)₂ (<b>4</b>) (tmpa = tris­(2-pyridyl­methyl)­amine, L¹ = chloranilic acid, L² = 2,5-dihydroxy-1,4-benzoquinone, L³ = (2,5-di-[2-(methoxy)-anilino]-1,4-benzoquinone, L⁴ = azophenine) were synthesized from copper­(II) salts, tmpa, and the bridging quinonoid ligands in the presence of a base. X-ray structural characterization of the complexes showed a distorted octahedral environment around the copper­(II) centers for the complexes <b>1</b>–<b>3</b>, the donors being the nitrogen atoms of tmpa, and the nitrogen or oxygen donors of the bridging quinones. In contrast, the copper­(II) centers in <b>4</b> display a distorted square-pyramidal coordination, where one of the pyridine arms of each tmpa remains uncoordinated. Bond-length analyses within the bridging ligand exhibit localization of the double bonds inside the bridge for <b>1</b>–<b>3</b>. In contrast, complete delocalization of double bonds within the bridging ligand is observed for <b>4</b>. Temperature-dependent magnetic susceptibility measurements on the complexes reveal an antiferromagnetic coupling between the copper­(II) ions. The strength of antiferromagnetic coupling was observed to depend on the energy of the HOMO of the bridging quinone ligands, with exchange coupling constants <i>J</i> in the range between −23.2 and −0.6 cm^–1 and the strength of antiferromagnetic coupling of <b>4</b> > <b>3</b> > <b>2</b> > <b>1</b>. Broken-symmetry density functional theory calculations (DFT) revealed that the orientation of magnetic orbitals in <b>1</b> and <b>2</b> is different than that in <b>3</b> and <b>4</b>, and this results in two different exchange pathways. These results demonstrate how bridge-mediated spin–spin coupling in quinone-bridged metal complexes can be strongly tuned by a rational design of the bridging ligand employing the [O] for [NR] isoelectronic analogy