Conversion from Heterometallic to Homometallic Metal-Organic Frameworks.

Two new heterometallic metal-organic frameworks (MOFs), LnZnTPO 1 and 2, and two homometallic MOFs, LnTPO 3 and 4 (Ln=Eu for 1 and 3, and Tb for 2 and 4; H3 TPO=tris(4-carboxyphenyl)phosphine oxide) were synthesized, and their structures and properties were analyzed. They were prepared by solvothermal reaction of the C3 -symmetric ligand H3 TPO with the corresponding metal ion(s) (a mixture of Ln3+ and Zn2+ for 1 and 2, and Ln3+ alone for 3 and 4). Single-crystal XRD (SXRD) analysis revealed that 1 and 3 are isostructural to 2 and 4, respectively. TGA showed that the framework is thermally stable up to about 400 °C for 1 and 2, and about 450 °C for 3 and 4. PXRD analysis showed their pore-structure distortions without noticeable framework-structure changes during drying processes. The shapes of gas sorption isotherms for 1 and 3 are almost identical to those for 2 and 4, respectively. Solvothermal immersion of 1 and 2 in Tb3+ and Eu3+ solutions resulted in the framework metal-ion exchange affording 4 and 3, respectively, as confirmed by photoluminescence (PL), PXRD, IR, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and energy-dispersive X-ray (EDX) analyses.

Reversible crystal-to-amorphous structural transformations and magnetic variations in single end-on azide-bridged MII (M = Mn, Ni) coordination polymers.

MII (M = Mn, Ni) coordination frameworks, singly linked by end-on azide ligands, were prepared by employing the long, flexible spacer ligand, p-XBP4. These two-dimensional layer structures underwent reversible crystal-to-amorphous phase transformations during the hydration-dehydration process. Moreover, the magnetic nature changes from antiferromagnetic to ferromagnetic coupling when moving from Mn to Ni.

Control of Interchain Antiferromagnetic Coupling in Porous Co(II)-Based Metal-Organic Frameworks by Tuning the Aromatic Linker Length: How Far Does Magnetic Interaction Propagate?

Three MOF-74-type Co(II) frameworks with one-dimensional hexagonal channels have been prepared. Co(II) spins in a chain are ferromagnetically coupled through carboxylate and phenoxide bridges. Interchain antiferromagnetic couplings via aromatic ring pathways operate over a Co-Co length shorter than ∼10.9 Å, resulting in a field-induced metamagnetic transition, while being absent over lengths longer than ∼14.7 Å.

Custom Coordination Environments for Lanthanoids: Tripodal Ligands Achieve Near-Perfect Octahedral Coordination for Two Dysprosium-Based Molecular Nanomagnets.

Controlling the coordination sphere of lanthanoid complexes is a challenging critical step toward controlling their relaxation properties. Here we present the synthesis of hexacoordinated dysprosium single-molecule magnets, where tripodal ligands achieve a near-perfect octahedral coordination. We perform a complete experimental and theoretical investigation of their magnetic properties, including a full single-crystal magnetic anisotropy analysis. The combination of electrostatic and crystal-field computational tools (SIMPRE and CONDON codes) allows us to explain the static behavior of these systems in detail.

Phase Transformation, Exceptional Quenching Efficiency, and Discriminative Recognition of Nitroaromatic Analytes in Hydrophobic, Nonporous Zn(II) Coordination Frameworks.

Five-fold interpenetrated Zn(II) frameworks (1 and 2) have been prepared, and an irreversible phase transformation from 1 to 2 is found to occur through a dissolution-recrystallization process. Compound 1 exhibits the highest quenching efficiency (>96%) for nitrobenzene at 7 ppm among luminescent coordination polymers. Selective discrimination of nitroaromatic molecules including o-nitrophenol (o-NP), p-nitrophenol (p-NP), 2,4-dinitrophenol (DNP), and 2,4,6-trinitrophenol (TNP) is realized in 1 and 2 as a result of the fact that the framework-analyte interaction affords characteristic emission signals. This observation is the first case of a nonporous coordination framework for such discriminative detection. Notably, significant hydrophobicity is evident in the framework 1 because of its surface roughness, which accounts for the enhanced quenching ability.

Slow relaxation dynamics of a mononuclear Er(iii) complex surrounded by a ligand environment with anisotropic charge density.

Two sets of isostructural mononuclear compounds, [Ln(LOMe)2(H2O)2](PF6) [1, Ln = Er; 3, Ln = Gd; LOMe = CpCo{P(O)(O(CH3))2}3] and Ln(LOMe)2(NO3) (2, Ln = Er and 4, Ln = Gd), are synthesized by self-assembly of the respective lanthanide ions and tripodal chelate ligands. The Ln ions are encircled by two LOMe ligands, and two water molecules or one nitrate anion. Each octacoordinated Ln center adopts a distorted square antiprism geometry. The Er complex (2) chelated by a nitrate anion shows slow dynamics in magnetic relaxation, diagnostic of a single-ion magnet. Quantum tunneling in 2 is effectively blocked by application of an external field. Weak intermolecular magnetic interactions occur in 2, and are supported by the magnetic behavior of 4. Chemical dilution of Er with the diamagnetic Y ion can nullify magnetic interactions and suppress quantum tunneling. Generation of slow relaxation dynamics in the Er system is related to the anisotropic charge distribution supplied by the coordination of ligands with different charge densities, as observed in the Dy analogue. This suggests that magnetic anisotropy arises in a coordination system when an anisotropic lanthanide ion (Dy and Er) is surrounded by a ligand environment with anisotropic charge density, resulting in slow magnetic relaxation.

Luminescent Metal-Organic Framework Sensor: Exceptional Cd2+ Turn-On Detection and First In Situ Visualization of Cd2+ Ion Diffusion into a Crystal.

With regard to fluorescence quenching commonly observed during metal-ion detection, "turn-on" chemical sensing has been rarely reported, but could be extremely important because it facilitates the selective recognition of target objects of interest against a dark background. A metal-organic framework (MOF) chemosensor has been prepared that serves as an efficient platform for the selective detection of Cu2+ and Cd2+ ions over other metal ions. In particular, this framework shows the highest fluorescence enhancement (≈60-fold relative to Cd-free MOF) for the hazardous metal ion Cd2+ among luminescent MOFs and displays excellent reusability in repeated cycles. The direct diffusion of Cd2+ into the crystal pores has also been visualized for the first time.

Fine-Tuning of the Carbon Dioxide Capture Capability of Diamine-Grafted Metal-Organic Framework Adsorbents Through Amine Functionalization.

A combined sonication and microwave irradiation procedure provides the most effective functionalization of ethylenediamine (en) and branched primary diamines of 1-methylethylenediamine (men) and 1,1-dimethylethylenediamine (den) onto the open metal sites of Mg2 (dobpdc) (1). The CO2 capacities of the advanced adsorbents 1-en and 1-men under simulated flue gas conditions are 19 wt % and 17.4 wt %, respectively, which are the highest values reported among amine-functionalized metal-organic frameworks (MOFs) to date. Moreover, 1-den exhibits both a significant working capacity (12.2 wt %) and superb CO2 uptake (11 wt %) at 3 % CO2 . Additionally, this framework showcases the superior recyclability; ultrahigh stability after exposure to O2 , moisture, and SO2 ; and exceptional CO2 adsorption capacity under humid conditions, which are unprecedented among MOFs. We also elucidate that the performance of CO2 adsorption can be controlled by the structure of the diamine ligands grafted such as the number of amine end groups or the presence of side groups, which provides the first systematic and comprehensive demonstration of fine-tuning of CO2 uptake capability using different amines.

Tuning of chain chirality by interchain stacking forces and the structure-property relationship in coordination systems constructed by meridional FeIII cyanide and MnIII Schiff bases.

We synthesized six Fe(iii)-Mn(iii) bimetallic compounds by self-assembling the newly developed mer-Fe cyanide PPh4[Fe(Clqpa)(CN)3]·H2O (1) and PPh4[Fe(Brqpa)(CN)3]·H2O (2) with Mn Schiff base Mn(5-Xsalen)+ cations. These compounds include [Fe(Xqpa)(CN)3][Mn(5-Ysalen)]·pMeOH·qH2O [qpaH2 = N-(quinolin-8-yl)picolinamide; salen = N,N'-ethylenebis(salicylideneiminato) dianion; X = Cl, Y = H (3); X = Cl, Y = Br (4); X = Br, Y = H (5); X = Br, Y = F (6); X = Br, Y = Cl (7); X = Br, Y = Br (8)]. When precursor 1 was used, compounds 3 and 4 were isolated to give a dinuclear entity and a linear chain structure, respectively. The reaction of precursor 2 with the Schiff bases afforded four linear Fe(iii)-Mn(iii) chain complexes. Chain chirality with P- and M-helicity emerges in 4, 7, and 8, while 5 exhibits chain helicity opposite to the previous chain complexes and 6 presents no chain helicity. Such a structural feature is heavily dependent on the interchain π-π contacts and the Fe precursor bridging unit. Chiral induction from a local ethylenediamine link of Y-salen is propagated over the chain via noncovalent π-π interactions. All the bimetallic compounds show antiferromagnetic interactions transmitted by the cyanide linkage. A field-induced metamagnetic transition is involved in 4, 7, and 8, while a field-induced two-step transition is evident in 6. From a magnetostructural viewpoint, the coupling constant is primarily governed by the Mn-Nax-Cax angle (ax = axial) in the bimetallic chain complexes composed of mer-Fe(iii) tricyanides, although the torsion angle plays a role.

Cost-Effective, High-Performance Porous-Organic-Polymer Conductors Functionalized with Sulfonic Acid Groups by Direct Postsynthetic Substitution.

We demonstrate the facile microwave-assisted synthesis of a porous organic framework 1 and the sulfonated solid (1S) through postsubstitution. Remarkably, the conductivity of 1S showed an approximately 300-fold enhancement at 30 °C as compared to that of 1, and reached 7.72×10-2  S cm-1 at 80 °C and 90 % relative humidity. The superprotonic conductivity exceeds that observed for any conductive porous organic polymer reported to date. This material, which is cost-effective and scalable for mass production, also revealed long-term performance over more than 3 months without conductivity decay.

Switching of Slow Magnetic Relaxation Dynamics in Mononuclear Dysprosium(III) Compounds with Charge Density.

The symmetry around a Dy ion is recognized to be a crucial parameter dictating magnetization relaxation dynamics. We prepared two similar square-antiprismatic complexes, [Dy(LOMe)2(H2O)2](PF6) (1) and Dy(LOMe)2(NO3) (2), where LOMe = [CpCo{P(O)(O(CH3))2}3], including either two neutral water molecules (1) or an anionic nitrate ligand (2). We demonstrated that in this case relaxation dynamics is dramatically affected by the introduction of a charged ligand, stabilizing the easy axis of magnetization along the nitrate direction. We also showed that the application of either a direct-current field or chemical dilution effectively stops quantum tunneling in the ground state of 2, thereby increasing the relaxation time by over 3 orders of magnitude at 3.5 K.

Adsorption of Carbon Dioxide on Unsaturated Metal Sites in M2 (dobpdc) Frameworks with Exceptional Structural Stability and Relation between Lewis Acidity and Adsorption Enthalpy.

A series of metal-organic frameworks (MOFs) M2 (dobpdc) (M=Mn, Co, Ni, Zn; H4 dobpdc=4,4'-dihydroxy-1,1'-biphenyl-3,3'-dicarboxylic acid), with a highly dense arrangement of open metal sites along hexagonal channels were prepared by microwave-assisted or simple solvothermal reactions. The activated materials were structurally expanded when guest molecules including CO2 were introduced into the pores. The Lewis acidity of the open metal sites varied in the order MnZn, as confirmed by C=O stretching bands in the IR spectra, which are related to the CO2 adsorption enthalpy. DFT calculations revealed that the high CO2 binding affinity of transition-metal-based M2 (dobpdc) is primarily attributable to the favorable charge transfer from CO2 (oxygen lone pair acting as a Lewis base) to the open metal sites (Lewis acid), while electrostatic effects, the underlying factor responsible for the particular order of binding strength observed across different transition metals, also play a role. The framework stability against water coincides with the order of Lewis acidity. In this series of MOFs, the structural stability of Ni2 (dobpdc) is exceptional; it endured in water vapor, liquid water, and in refluxing water for one month, and the solid remained intact on exposure to solutions of pH 2-13. The DFT calculations also support the experimental finding that Ni2 (dobpdc) has higher chemical stability than the other frameworks.

Exceptional CO2 working capacity in a heterodiamine-grafted metal-organic framework.

An amine-functionalized metal-organic framework (MOF), dmen-Mg2(dobpdc) (dmen = N,N-dimethylethylenediamine), which contains a heterodiamine with both primary and tertiary amines, was prepared via a post-synthetic method. This material exhibits a significant selectivity factor for CO2 over N2 that is commensurate with top-performing MOFs. It is remarkable that the solid is fully regenerated under vacuum or flowing Ar at low desorption temperatures, and following this can take up CO2 at more than 13 wt%. An exceptionally high working capacity is achieved at low regeneration temperatures and after exposure to humid conditions, which are important parameters for a real post-combustion CO2 capture process.

Synthesis, crystal structures, and magnetic properties of cyanide-bridged W(V)Mn(III) anionic coordination polymers containing divalent cationic moieties: slow magnetic relaxations and spin crossover phenomenon.

Two trimetallic coordination complexes were prepared by self-assembly of [W(CN)8](3-) and the Mn(III) Schiff base followed by the addition of a Zn(II) or Fe(II) cationic unit. The octacyanotungstate connects neighboring Mn(III) centers to form a one-dimensional chain. The anionic chain requires cationic units of Zn(II) or Fe(II) to maintain charge balance in the structure. The Zn-containing complex shows ferrimagnetic behavior originating from the antiparallel alignment of W(V) and Mn(III) spins within the chain, which leads to slow magnetic relaxation at low temperatures. For the Fe(II)-containing compound, Fe(II) moieties are integrated into the ferrimagnetic chains, altering their spin states depending on the temperature. It appears that the coexistence of high- and low-spin states in the low temperature regime is responsible for the slower and faster relaxations of the magnetization.

Synthesis, structures, and magnetic properties of end-to-end azide-bridged manganese(III) chains: elucidation of direct magnetostructural correlation.

The two one-dimensional chain compounds [Mn(L1)(N3)]·H2O (1·H2O; H2L1 = 2,2'-((1E,1'E)-ethane-1,2-diylbis(azan-1-yl-1-ylidene))bis(phenylmethan-1-yl-1-ylidene)diphenol) and [Mn(L2)(N3)] (2; H2L2 = 2,2'-((1E,1'E)-2,2-dimethylpropane-1,3-diyl)bis(azan-1-yl-1-ylidene)-bis(phenylmethan-1-yl-1-ylidene)diphenol) bridged by single end-to-end azides were prepared via a self-assembly process. Each Mn(III) ion exhibits a characteristic Jahn-Teller elongation along the chain direction. For both compounds, antiferromagnetic interactions between Mn(III) spins within a chain are transmitted through the azide ligands, together with the apparent occurrence of spin canting at low temperatures. Remarkably, the coupling constants (J) for 1 and 2 exceed those reported for end-to-end azide-linked Mn(III) systems. A systematic magnetostructural relationship based on the torsion angle is established in terms of the torsion angle Mn-N(ax)···N(ax)-Mn (ax = axial) for the first time.

Dehydration-triggered magnetic phase conversion in the porous Cu(II)Mn(III) metal-organic framework.

Dehydration of the three-dimensional Cu(II)-Mn(III) coordination network undergoes a dramatic magnetic phase transformation from a paramagnetic state to a long-range magnetic ordered phase with glassy behavior. The gas adsorption behavior and re-entrant spin glass character are uniquely apparent in the dehydrated sample.

[W(CN)6(L)](1-/2-) (L = bidentate ligand) as a useful building unit to construct molecule-based magnetic systems.

Metal ions heavier than the 3d metals have attracted increasing attention due to their strong magnetic exchange coupling, arising from the diffuse nature of the extended valence orbitals of the 4d and 5d elements and the involvement of a large magnetic anisotropy contingent on their strong spin-orbit coupling. [W(CN)6(L)](1-/2-) (L = 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen)) serves as a suitable building block for constructing molecule-based magnetic systems. Discrete molecular entities and one-dimensional chains are preferably obtained when the restricted paramagnetic precursor [W(CN)6(bpy)](-) encounters metal counterparts with the available coordination sites. The bimetallic magnetic assemblies exhibit a variety of magnetic features, along with a magnetostructural correlation. These include slow relaxation of magnetization, typical for single-molecule magnets and single-chain magnets, spin-canting, and metamagnetism. The two-dimensional structure is stabilized by using the reduced [W(CN)6(bpy)](2-) complex. In this perspective article, detailed discussions of molecular materials based on the W(V) ion are reviewed.

Cyanide-bridged W(V)Mn(III) bimetallic chains composed of a blocked W hexacyanide precursor: geometry-related magnetic couplings and magnetostructural correlation.

Five one-dimensional bimetallic W(V)Mn(III) complexes 1-5, consisting of [W(CN)6(bpy)](-) anions and [Mn(Schiff base)](+) cations, were prepared. The central coordination geometry around each W atom is determined as a distorted dodecahedron (DD) for 1 and 2, and a distorted square antiprism (SAPR) for 3-5. Magnetic analyses demonstrate that compounds 1, 4, and 5 exhibit antiferromagnetic interactions between magnetic centers, which are different from the ferromagnetic couplings in 2 and 3. For the distorted DD geometry, the Mn-N(ax) (ax = axial) bond length increases when moving from 1 to 2, with the Mn-N(ax)-C(ax) angle remaining constant. The elongation of the bond length is responsible for the reduction in orbital overlap and consequent ferromagnetic coupling in 2. In comparison, for 3-5 with the distorted SAPR geometry, given that the Mn-N(ax) bond lengths are similar across all the samples, the increase in the Mn-N(ax)-C(ax) angles accounts for the enhanced magnetic strength. Notably, a correlation between structure and magnetic exchange coupling is established for the first time in W(V)Mn(III) bimetallic systems based on the [W(CN)6(bpy)](-) precursor.

Syntheses, structures, and magnetic properties of cyano- and phenoxide-bridged Fe(III)-Mn(III) tetrameric assemblies formed by blocked fac-Fe tricyanide with aliphatic rings.

Three tetranuclear clusters [(Tp(Me,mt3))Fe(CN)3Mn(L)]2 (1, L = 5-Clacphmen; 2, L = 5-Clsalen; 3, L = 5-MeOsalen; Tp(Me,mt3) = hydrotris(3-methyl-4,5-propylene-5-methylpyrazol-1-yl)borate) were prepared by assembling the fac-Fe tricyanide with the corresponding Mn Schiff bases. The assembled molecules are linked by cyanide and phenoxide bridges. Weak π-π contacts between molecules are evident in these clusters. Compounds 1-3 exhibit slow relaxation of the magnetization. The phenoxide linkers mediate ferromagnetic coupling between the Mn centers, which is ascribed to the long axial Mn-O* length. The overall magnetic exchange coupling nature of the Fe-C≡N-Mn route is accounted for by the important structural parameters of bridging pathways such as Mn-N(cyano) length, Mn-N(cyano)-C(cyano) angle, and C(eq)-Fe···Mn-N(eq) (eq = equatorial) torsion angle.

Synthesis, structures and magnetic characterizations of isostructural tetranuclear Ln4 clusters (Ln = Dy, Ho, and Eu).

Isostructural tetranuclear clusters [Ln4(salen)6]·xH2O [Ln = Dy, 1·5.5H2O; Ho, 2·4.6H2O; Eu, 3·5.2H2O; salen = N,N'-ethylenebis(salicylideneiminato)dianion] were prepared by self-assembling the corresponding lanthanide ions and a quadridentate Schiff base. Interestingly, the Ln ions are surrounded by the N- and O-donors of the Schiff bases, leading to seven- and eight-coordinate environments. The heptacoordinated Ln centers adopt a distorted capped trigonal prism, while the octacoordinated Ln atoms are in a dodecahedral disposition. The Dy complex exhibits slow magnetic relaxation, characteristic of a single-molecule magnet. Two relaxation modes in the Dy system are evident when H(dc) = 1.4 kG is applied, which is attributable to the existence of the dissimilar coordination geometries around Dy. In comparison, the Ho and Eu analogues were magnetically inspected, displaying no typical slow magnetic relaxation. These findings elucidate that the metal component in the system plays a central role in the occurrence of the magnetization relaxation process. The pronounced long-range order may contribute to intrachain exchange couplings and through-space dipolar interactions between adjacent chains.