Enhanced hydrogen uptake of dihydrogen complex via porous materials support.

This research focuses on enhancing H2 adsorption by using the [Mo(PCy3)2(CO)3] complex supported on porous materials such as silica gel and mesoporous carbon. The study reports a significant increase in hydrogen adsorption capacity, reaching up to 9.3 times that of the bulk complex. This improvement suggests that using mesoporous materials as supports for the [Mo(PCy3)2(CO)3] complex enhances the accessibility of H2 gas to its open-metal sites.

Quinoid-Based Three-Dimensional Metal-Organic Framework Fe2(dhbq)3: Porosity, Electrical Conductivity, and Solid-State Redox Properties.

We report the synthesis, characterization, and electronic properties of the quinoid-based three-dimensional metal-organic framework [Fe2(dhbq)3]. The MOF was synthesized without using cations as a template, unlike other reported X2dhbq3-based coordination polymers, and the crystal structure was determined by using single-crystal X-ray diffraction. The crystal structure was entirely different from the other reported [Fe2(X2dhbq3)]2-; three independent 3D polymers were interpenetrated to give the overall structure. The absence of cations led to a microporous structure, investigated by N2 adsorption isotherms. Temperature dependence of electrical conductivity data revealed that it exhibited a relatively high electrical conductivity of 1.2 × 10-2 S cm-1 (Ea = 212 meV) due to extended d-π conjugation in a three-dimensional network. Thermoelectromotive force measurement revealed that it is an n-type semiconductor with electrons as the majority of charge carriers. Structural characterization and spectroscopic analyses, including SXRD, Mössbauer, UV-vis-NIR, IR, and XANES measurements, evidenced the occurrence of no mixed valency based on the metal and the ligand. [Fe2(dhbq)3] upon incorporating as a cathode material for lithium-ion batteries engendered an initial discharge capacity of 322 mAh/g.

Porous Mn2+ Magnet with a Pt-Cl Framework: Correlation between Water Vapor Adsorption/Desorption and Slow Magnetic Relaxation.

We report the water adsorption/desorption behavior and dynamic magnetic properties of the Pt-Cl chain complex [{[Pt(en)2 ][PtCl2 (en)2 ]}3 ][{(MnCl5 )Cl3 }2 ] ⋅ 12H2 O (1). Upon heating 1 in a vacuum, we obtained the dehydrated form [{[Pt(en)2 ][PtCl2 (en)2 ]}3 ][{(MnCl5 )Cl3 }2 ] (1DH). The framework structures of 1 and 1DH are identical, and both complexes underwent slow magnetic relaxation. However, the magnetic relaxation times for 1DH were shorter than those for 1, meaning that the dynamic magnetic properties were controlled upon water vapor adsorption/desorption. From detailed analyses of the dynamic magnetic behavior, a phonon-bottleneck effect contributes to the magnetic relaxation processes. We discuss the mechanism for the changes in the magnetic relaxation processes upon dehydration in terms of the heat capacity and thermal conductivity.

Syntheses, Structures, and Properties of Coordination Polymers with 2,5-Dihydroxy-1,4-Benzoquinone and 4,4'-Bipyridyl Synthesized by In Situ Hydrolysis Method.

The coordination polymers (CPs) with binary ligands, including 2,5-dihydroxy-1,4-benzoquinone (H2DHBQ) and 4,4'-bipyridyl (bpy), were synthesized using in situ hydrolysis of 2,5-dimethoxy-1,4-benzoquinone (DMBQ). Three kinds of CPs were obtained depending on the metal ions. For M = Mn and Zn, a 1D zigzag chain structure with cis conformation ( cis-1D-M) was obtained, whereas Co, Ni, and Cu compounds afforded a 2D net structure with trans conformation (trans -2D-M) with a 1D pore. A linear chain structure was also obtained for M = Cu. Magnetic susceptibility (χM T) at 300 K in cis -1D-Mn and trans -2D-Co was evaluated to be 4.421 and 2.950 cm3 K mol-1, respectively, indicating that both compounds are in the high-spin state. According to the N2 adsorption isotherms at 77 K, trans -2D-Ni showed microporosity with the BET surface area of 177 m2 g-1, whereas the isomorphic trans -2D-Co rarely adsorbed N2 at 77 K. This phenomenon was explained by the difference of diffusion kinetics of the adsorbent molecules, which was supported by the CO2 adsorption isotherms at 195 K. The optical band gaps of cis -1D-Mn, cis -1D-Zn, trans -2D-Co, and trans -2D-Ni were estimated to be 1.6, 1.8, 1.0, and 1.1 eV, respectively, by using UV-vis-NIR spectroscopy.

An electrically conductive metallocycle: densely packed molecular hexagons with π-stacked radicals.

Electrical conduction among metallocycles has been unexplored because of the difficulty in creating electronic transport pathways. In this work, we present an electrocrystallization strategy for synthesizing an intrinsically electron-conductive metallocycle, [Ni6(NDI-Hpz)6(dma)12(NO3)6]·5DMA·nH2O (PMC-hexagon) (NDI-Hpz = N,N'-di(1H-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxdiimide). The hexagonal metallocycle units are assembled into a densely packed ABCABC… sequence (like the fcc geometry) to construct one-dimensional (1D) helical π-stacked columns and 1D pore channels, which were maintained under the liberation of H2O molecules. The NDI cores were partially reduced to form radicals as charge carriers, resulting in a room-temperature conductivity of (1.2-2.1) × 10-4 S cm-1 (pressed pellet), which is superior to that of most NDI-based conductors including metal-organic frameworks and organic crystals. These findings open up the use of metallocycles as building blocks for fabricating conductive porous molecular materials.

Reversible hydrogen adsorption at room temperature using a molybdenum-dihydrogen complex in the solid state.

Reversible H2 storage under mild conditions is one of the most important targets in the field of materials chemistry. Dihydrogen complexes are attractive materials for this target because they possess moderate adsorption enthalpy as well as adsorption without cleavage of the H-H bond. In spite of these advantages, H2 adsorption studies of dihydrogen complexes in the solid state are scarce. We herein present H2 adsorption properties of the 16-electron precursor complex ([Mo(PCy3)2(CO)3]) in the solid state synthesized by two procedures. One is the direct synthesis under an Ar atmosphere (1), and the other is removal of the N2-adduct under vacuum (2). 2 showed ideal Langmuir type reversible ad/desorption of H2 above room temperature, whereas 1 showed irreversible adsorption. The adsorption enthalpy of 2 was larger than that in THF solution. Using DFT calculation, this difference was explained by the absence of the agostic interaction in the solid state.

Electron-Conductive Metal-Organic Framework, Fe(dhbq)(dhbq = 2,5-Dihydroxy-1,4-benzoquinone): Coexistence of Microporosity and Solid-State Redox Activity.

Redox-active metal-organic frameworks (MOFs) have great potential for use as cathode materials in lithium-ion batteries (LIBs) with large capacities because the organic ligands can undergo multiple-electron redox processes. However, most MOFs are electrical insulators, limiting their application as electrode materials. Here, we report an electron-conductive MOF with a 2,5-dihydroxy-1,4-benzoquinone (dhbq) ligand, Fe(dhbq). This compound had an electrical conductivity of 5 × 10-6 S cm-1 at room temperature due to d-π interactions between the Fe ion and the ligand and the permanent microporosity. Fe(dhbq) had an initial discharge capacity of 264 mA h g-1, corresponding to the two-electron redox process of dhbq.

Simultaneous manifestation of metallic conductivity and single-molecule magnetism in a layered molecule-based compound.

Single-molecule magnets (SMMs) show superparamagnetic behaviour below blocking temperature at the molecular scale, so they exhibit large magnetic density compared to the conventional magnets. Combining SMMs and molecular conductors in one compound will bring about new physical phenomena, however, the synergetic effects between them still remain unexplored. Here we present a layered molecule-based compound, ß''-(BEDO-TTF)4 [Co(pdms)2]·3H2O (BO4), (BEDO-TTF (BO) and H2pdms are bis(ethylenedioxy)tetrathiafulvalene and 1,2-bis(methanesulfonamido)benzene, respectively), which was synthesized by using an electrochemical approach and studied by using crystal X-ray diffraction. This compound simultaneously exhibited metallic conductivity and SMM behaviour up to 11 K for the first time. The highest electrical conductivity was 400-650 S cm-1 at 6.5 K, which is the highest among those reported so far for conducting SMM materials. Furthermore, antiferromagnetic ordering occurred below 6.5 K, along with a decrease in conductivity, and the angle-independent negative magnetoresistance suggested an effective electron correlation between the conducting BO and Co(pdms)2 SMM layers (d-π interactions). The strong magnetic anisotropy and two-dimensional conducting plane play key roles in the low-temperature antiferromagnetic semiconducting state. BO4 is the first compound exhibiting antiferromagnetic ordering among SMMs mediated by π-electrons, demonstrating the synergetic effects between SMMs and molecular conductors.

Isostructural M(ii) complexes (M = Mn, Fe, Co) with field-induced slow magnetic relaxation for Mn and Co complexes.

We herein report the synthetic, structural, theoretical, and magnetic studies on three isostructural complexes, [M(L)2(CH3OH)2] (M = Mn (Mn), Fe (Fe), and Co (Co); HL = 2,6-bis(pyrazole-1-yl)pyridine-4-carboxylic acid). From single crystal X-ray crystallography, it is found that the complexes crystallized in the same space group (C2/c) and had seven-coordinate pentagonal bipyramidal structures. From direct current (dc) and alternating current (ac) magnetic susceptibility measurements, Mn and Co were found to undergo field-induced slow magnetic relaxation with two relaxation pathways. To elucidate the origin of the slow magnetic relaxation phenomena of Mn, electron paramagnetic resonance (EPR) measurements and theoretical calculations were performed. The EPR measurements were performed on polycrystalline powder samples, and the following parameters were obtained by simulating the EPR data: giso = 2.00 and small zero field splitting parameter D = -0.13 cm-1. To the best of our knowledge, this is the first example of a seven-coordinate mononuclear Mn(ii) complex undergoing slow magnetic relaxation.