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.

Spin qubits of Cu(II) doped in Zn(II) metal-organic frameworks above microsecond phase memory time.

With the aim of creating Cu(II) spin qubits in a rigid metal-organic framework (MOF), this work demonstrates a doping of 5 %, 2 %, 1 %, and 0.1 % mol of Cu(II) ions into a perovskite-type MOF [CH6 N3 ][ZnII (HCOO)3 ]. The presence of dopant Cu(II) sites are confirmed with anisotropic g-factors (gx =2.07, gy =2.12, and gz =2.44) in the S=1/2 system by experimentally and theoretically. Magnetic dynamics indicate the occurrence of a slow magnetic relaxation via the direct and Raman processes under an applied field, with a relaxation time (τ) of 3.5 ms (5 % Cu), 9.2 ms (2 % Cu), and 15 ms (1 % Cu) at 1.8 K. Furthermore, pulse-ESR spectroscopy reveals spin qubit properties with a spin-spin relaxation (phase memory) time (T2 ) of 0.21 µs (2 %Cu), 0.39 µs (1 %Cu), and 3.0 µs (0.1 %Cu) at 10 K as well as Rabi oscillation between MS =±1/2 spin sublevels. T2 above microsecond is achieved for the first time in the Cu(II)-doped MOFs. It can be observed at submicrosecond around 50 K. These spin relaxations are very sensitive to the magnetic dipole interactions relating with cross-relaxation between the Cu(II) sites and can be tuned by adjusting the dopant concentration.

Chemical pressure-induced PtIII-I Mott-Hubbard nanowire, [Pt(en)2I](Asp-Cn)2·H2O (13 ≤ n), detected via polarized infrared spectroscopy.

The electronic states of iodo-bridged platinum nanowire complexes have been studied using polarized FT-IR spectroscopy. The N-H symmetrical stretching mode was found to be highly sensitive to the electronic states, distinguishing mixed-valence (MV) and averaged-valence (AV) states. The first Pt(III) nanowire complexes have been realized by the chemical pressures of the counter-anions.

Hexagonal crystalline Magnus' green salt analogues prepared from hydroxy-functionalised Pt and Pd complexes.

New Magnus' green salt (MGS) analogues, [M(dabdOH)2][MCl4]·2H2O (dabdOH = (2S,3S)-2,3-diaminobutane-1,4-diol; M = Pd (1) and M = Pt(2)), in which [M(dabdOH)2]2+ and [MCl4]2- are stacked alternately to form linear chains, were obtained as hexagonal plate crystals. The hexagonal shape and large crystal size are unprecedented features as MGS analogues. An unusual trigonal grade separation of chain complexes has been revealed by the structural analysis. 1 and 2 exhibited remarkable yellow and pink colours, respectively, which are derived from weak M⋯M interactions. The dabdOH ligand, which has an additional hydrogen donor group (hydroxy group), produces a multiple-hydrogen-bond network. The combination of intrachain and interchain hydrogen bonds gives a two-dimensional (2D) hydrogen-bond sheet, and each 2D sheet is indirectly connected by hydrogen bonds via lattice water molecules. The OH-functionalised ligand greatly increases the hydrophilicity of the MGS analogues and yields the largest single crystals of all MGS analogues reported so far. The trigonal grade-separated chain structure is likely due to the geometric matching between the periodicity of chains and the short axis width of the chain. This strategy opens up new insight for preparing large crystals of MGS analogues and for constructing trigonal grade-separated nanowires in molecular crystals.

Slow magnetic relaxation in a ferromagnetic CuII chain complex, induced by a phonon bottleneck effect.

The first slow magnetic relaxation in a ferromagnetic Cu(II) chain compound, Cu(dipic)(OH2)2 (dipicH2 = pyridine-2,6-dicarboxylic acid), induced by a phonon bottleneck effect under a magnetic field of 0.6 T, with a relaxation time of 2.2 s at 2.8 K, was observed.

Single-Crystal Structures of Benzenehexathiol and Its Disulfide Forms.

Oligothiols are useful as building blocks in the construction of disulfide-based macrocycles and polymers or as ligands for coordination polymers. Above all, benzenehexathiol (BHT) is a particularly important molecule, as it is used to construct conductive two-dimensional MOFs. Despite the desire to clarify its structure and isolate it to high purity, the chemical instability of BHT has hampered single-crystal X-ray structure analysis of intact BHT. In addition, the synthesis of discrete disulfide molecules of BHT has not been reported. Here, we succeed in obtaining the single crystals of intact BHT, which is analyzed by single crystal X-ray structure analysis. Furthermore, the structures of a group of molecules with intermolecular disulfide bonds (BHT·4im and BHT2·2TBA, im = imidazole, TBA = tetrabutylammonium cation) obtained by processing BHT in the presence of bases are determined.

Spin dynamics in a Heisenberg weak antiferromagnetic chain of an iodide-bridged Cu(II) complex.

[CuII(chxn)2I]I (chxn = 1R,2R-diaminocyclohexane) has been synthesized, which is the first report of an iodide-bridged Cu(II) chain structure. This chain compound shows S = 1/2 Heisenberg weak antiferromagnetism (J = -0.3 cm-1) and magnetic relaxation (τ = 43 ms at 1.8 K) with a Raman process in a static field.

Creation of a Field-Induced Co(II) Single-Ion Magnet by Doping into a Zn(II) Diamagnetic Metal-Organic Framework.

The combination of single-ion magnets (SIMs) and metal-organic frameworks (MOFs) is expected to produce new quantum materials. The principal issue to be solved in this regard is the development of new strategies for the synthesis of SIM-MOFs. This work demonstrates a new simple strategy for the synthesis of SIM-MOFs where a diamagnetic MOF is used as the framework into which the SIM sites are doped. 1, 0.5, and 0.2 mol% of the Co(II) ions are doped into the Zn(II) sites of [CH6 N3 ][ZnII (HCOO)3 ]. The doped Co(II) sites in the MOFs perform as SIM with a positive D term of zero-field splitting. The longest magnetic relaxation time is 150 ms (0.2 mol% Co) at 1.8 K under a static field of 0.1 T. Temperature dependency of the relaxation time suggests suppressing magnetic relaxation by reduction of spin-spin interaction upon doping in the rigid framework. Thus, this work represents a proof of concept for the creation of a single-ion doped magnet in the MOF. This simple synthetic strategy will be widely applied for the creation of quantum magnetic materials.

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.

Deprotonation-Induced Color Modulation in N,N'-Dihydroxynaphthalenediimide-Based Organic Crystals.

N,N'-dihydroxy-1,4,5,8-naphthalenetetracarboxdiimide (NDI-(OH)2 ) has attracted much attention in recent years, because its doubly deprotonated state, (O-NDI-O)2- , has metal-coordination ability and characteristic electronic transition useful for designing electronic and optical functions. In contrast, a molecular crystal with the mono-deprotonated (HO-NDI-O)- ion remains unknown. We herein report an organic crystal containing non-disproportionated (HO-NDI-O)- ions, which are connected by very strong O-H-O hydrogen bonds. Its lowest energy absorption band (450 to 650 nm) is observed in between that of NDI-(OH)2 (380 nm) and isolated (O-NDI-O)2- (500 to 850 nm) species, consistent with the molecular orbital calculations. This absorption originates from the electronic transition from deprotonated imide-based orbitals to NDI-core orbitals, which can be influenced by the hydrogen bonds around imide group. Consequently, the optical properties of NDI-(OH)2 can be modulated by the stepwise deprotonation and hydrogen-bonding interactions.

Rupture of the internal carotid artery pseudoaneurysm resulting from fungal sinusitis.

Although vasculitis due to infection with fungi, including Aspergillus, causes aneurysm formation, reports of internal carotid artery aneurysm formation resulting from fungal sinusitis are few. We report on a patient who experienced massive epistaxis from rupture of an internal carotid artery pseudoaneurysm, caused by fungal sinusitis. We treated the aneurysm with endovascular coil embolization, followed by endoscopic sinus surgery to remove the fungal mass. Intraoperative findings included a torn internal carotid artery and exposure of the coil to the sinus. Performing endoscopic sinus surgery before the embolization procedure would have increased the risks of massive intraoperative bleeding and mortality. Even after achieving hemostasis, serious sequelae, such as cerebral infarction, might occur. In this type of case, otorhinolaryngologists and neurosurgeons should collaborate, and an aneurysm should be treated before endoscopic sinus surgery. Although the treatment strategy for fungal internal carotid artery aneurysms is controversial, this case suggested the use of the embolization procedure followed by endoscopic debridement and antifungal therapy to treat a pseudoaneurysm of the internal carotid artery caused by fungal sinusitis.

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.

Intramolecular Ferromagnetism in Di-Nuclear 3 d-Transition-Metal Single-Molecule Magnets by Pseudo-Serial Arrangement.

Di-nuclear citrate complexes, [CH6 N3 ]2 [M2 (citH)2 (H2 O)4 ] ⋅ 2H2 O (citH4 =citric acid; M=FeII (Fe-2), CoII (Co-2), and NiII (Ni-2)), are synthesized. The ligand, citH3- , is deprotonated only at the three carboxy groups, which is different from the previously reported tetra-nuclear structures with cit4- ligands. Magnetic measurements reveal that these complexes have intramolecular ferromagnetism with J=∼0 cm-1 (Ni-2), 0.02 cm-1 (Co-2), and 0.04 cm-1 (Fe-2). Co-2 and Fe-2 show slow magnetic relaxation, and are field-induced SMMs with activation energy of spin-reversal Ueff =27 cm-1 (Co-2) and 4.2 cm-1 (Fe-2). Density functional theory calculations indicate that the uniaxial anisotropy along the z-axis of each metal ion center forms the pseudo-serial arrangement, leading to intramolecular ferromagnetism via the magnetic dipole interaction. This work demonstrates the creation of ferromagnetic SMMs by the magnetic dipole engineering of 3d di-nuclear metal ion centers.

Hydrogen Bonding Propagated Phase Separation in Quasi-Epitaxial Single Crystals: A Pd-Br Molecular Insulator.

In condensed matter, phase separation is strongly related to ferroelasticity, ferroelectricity, ferromagnetism, electron correlation, and crystallography. These ferroics are important for nano-electronic devices such as non-volatile memory. However, the quantitative information regarding the lattice (atomic) structure at the border of phase separation is unclear in many cases. Thus, to design electronic devices at the molecular level, a quantitative electron-lattice relationship must be established. Herein, we elucidated a PdII-PdIV/PdIII-PdIII phase transition and phase separation mechanism for [Pd(cptn)2Br]Br2 (cptn = 1R,2R-diaminocyclopentane), propagated through a hydrogen-bonding network. Although the Pd···Pd distance was used to determine the electronic state, the differences in the Pd···Pd distance and the optical gap between Mott-Hubbard (MH) and charge-density-wave (CDW) states were only 0.012 Å and 0.17 eV, respectively. The N-H···Br···H-N hydrogen-bonding network functioned as a jack, adjusting the structural difference dynamically, and allowing visible ferroelastic phase transition/separation in a fluctuating N2 gas flow. Additionally, the effect of the phase separation on the spin susceptibility and electrical conductivity were clarified to represent the quasi-epitaxial crystals among CDW-MH states. These results indicate that the phase transitions and separations could be controlled via atomic and molecular level modifications, such as the addition of hydrogen bonding.

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.

Benzenetriimide-Based Molecular Conductor with Antiferro- to Ferromagnetic Switching Induced by Structural Change of π-stacked Array.

Benzenetriimide (BTI) is a promising building block for materials chemistry due to its characteristic 3-fold symmetry and redox properties, whereas little is known about its conductive and magnetic properties. In this study, we synthesized three charge-transfer complexes based on N,N',N''-trimethylbenzenetriimide (BTI-Me). One of the complexes contains isolated dimers of BTI-Me radical anion (BTI-Me⋅- ), while the other two have the infinite π-stacked array of BTI-Me with the formal charge of -0.5. The latter two complexes did not show metallic behavior but showed semiconducting behavior probably due to the characteristic insulation in one-dimensional electron system, so-called charge ordering and dimer-Mott insulation. The magnetic susceptibility of the complex in dimer-Mott state exhibits an unusual transition from antiferromagnetic to ferromagnetic spin states with the hysteresis loop of 15 K derived from the structural phase transition around 130 K. These properties were also supported by DFT calculations.

Ni(III) Mott-Hubbard-like State Containing High-Spin Ni(II) in a Semiconductive Bromide-Bridged Ni-Chain Compound.

Halogen-bridged linear chain metal complexes (MX-Chains) are fascinating compounds that have a quasi-one-dimensional (1D) electronic system. In this study, we synthesized the first Ni-based MX-Chain compound having hydroxy groups, i.e., [Ni(dabdOH)2Br]Br2·[Ni(dabdOHx)2Br]0.5·(2-PrOH)0.25·(MeOH)0.25 (1·solvent, x = ∼0.6, dabdOH = (2S,3S)-2,3-diaminobutane-1,4-diol). Single-crystal X-ray diffraction revealed that the MX-Chains in 1·solvent formed sheets and single-chain structures in the superlattice. It suggested an MH-like state, whereas the polarized reflection and Raman spectra suggested a CDW-like state. Magnetic and electron spin resonance measurements revealed that both high-spin Ni(II) (∼15%) and low-spin Ni(III) (∼85%) sites are present in the chain structures, i.e., the metal sites show mixed valency. Therefore, we concluded that 1·solvent adopts an intermediate state between the MH and CDW states. Moreover, a single crystal of 1·solvent exhibited semiconductive characteristics along the chain direction. This finding represents a new structural and electronic state of 1D electronic systems as well as MX-Chains.

Thermally induced electron-hole dissociation dynamics in quasi-one-dimensional bromo-bridged palladium(III) Mott-insulator [Pd(en)2Br](Suc-Cn)2·H2O (Cn-Y = dialkylsulfosuccinate; n = 5 and 6).

Current-voltage characteristics and dielectric properties were studied in bromo-bridged one-dimensional compounds, [Pd(en)2Br](Suc-C5)2·H2O, exhibiting mixed-valence and averaged valence (MV-AV) phase transition. In the AV phase, clear nonlinear current-voltage characteristics were observed. This phenomenon was explained by the thermally induced electron-hole separation assisted by an electric field. This mechanism was supported by the dielectric properties of [Pd(en)2Br](Suc-Cn)2·H2O (n = 5 and 6).

Endoscopic Endonasal Repair of the Orbital Medial Wall Fracture Utilising Nasal Septal Cartilage as the Reconstructive Material.

BACKGROUND: To repair orbital medial wall fractures, otorhinolaryngologists often use the silicone sheet technique by inserting an inverted U-shaped silicone sheet into the middle meatus after the removal of fractured bones, and packing gauze inside the silicone sheet for several days to fix the shape of the medial wall. However, this method does not sufficiently reduce the orbital content. OBJECTIVE: To describe the surgical procedure to repair medial wall fractures using nasal septal cartilage as the reconstructive material. METHODS: First, endoscopic septoplasty is performed. Although the correction of the septal deviation is performed to secure the operative field, the nasal septal cartilage, except the L-strut is resected simultaneously. After septoplasty, the fractured bones of the lamina papyracea are removed from the herniated orbital contents, and then the orbital contents can be reduced without resistance by pushing laterally. Subsequently, the cartilage is inserted beneath the fracture edges of the orbital medial wall with great care to avoid entrapping the orbital soft tissue and extraocular muscles. RESULTS: The cartilage can be placed appropriately along the medial wall of the orbit. CONCLUSION: This technique enables to repair most cases of orbital medial wall fractures using the endoscopic endonasal approach alone without alloplastic implants.