Control of the electronic and optical properties of aminoxyl radicals boron complexation.

Stable radicals have attracted increasing attention in recent years because of their unique electronic and optical characteristics. Aminoxyl radicals are one of the most widely studied stable radicals to date, but their applications in opto-functional materials have yet to be explored in detail. Our group previously reported the boron complexes of aminoxyl radicals exhibit near-infrared (NIR) absorption.

Controlling the gate-sorption properties of solid solutions of Werner complexes by varying component ratios.

Methods relying on the use of solid solutions can be used to produce solid materials having finely controlled physical properties. In the current investigation, we utilized this protocol to prepare solid solutions derived from two different Werner complexes in order to assess the effects of component ratios on acetone vapor adsorption properties. For this purpose, microcrystalline solid solutions with the basic elemental composition α-[Cu(PF6)2(py)4]x[Cu(CF3SO3)2(py)4]1-x (x = 0.

A Zn(ii) metal-organic framework with dinuclear [Zn(N-oxide)] secondary building units.

We report the synthesis, structural characterisation, and adsorption properties of a three-dimensional metal-organic framework [Zn(pydcao)(DMF)] (H2-pydcao = 3,5-pyridinedicarboxylic acid N-oxide) that has an unprecedented [Zn2(N-oxide)2] secondary building unit.

Supramolecular self-assembly for designing non-centrosymmetric crystals based on Keggin polyoxometallates and crown ether.

We report the synthesis of five novel crystals [(4-BrAni+)(DB[18]crown-6)]2[SMo12O402-]·2CH3CN (1), [(4-BrAni+)(B[18]crown-6)]2[SMo12O402-]·CH3CN (2), [(4-BrAni+)(B[18]crown-6)]3[PMo12O402-]·2CH3CN (3), [(3-AP+)3(B[18]crown-6)2][PMo12O403-] (4) and [NBu4+][(3-AP2+)(DB[30]crown-10)][PMo12O403-]·CH3CN (5) (4-BrAni+ = 4-bromoanilinium; B[18]crown-6 = benzo[18]-crown-6; DB[18]crown-6 = dibenzo[18]-crown-6; DB[30]crown-10 = dibenzo[30]-crown-10; 3-AP+ = 3-aminopyridinium; 3-AP2+ = 3-ammoniumpyridinium; NBu4+ = tetrabutylammonium). In order to construct non-centrosymmetric crystals, the five crystals were designed using a method to gradually introduce asymmetry into the building units. Crystal 1 was constructed with a symmetric supramolecular cation (SPC) [(4-BrAni+)(DB[18]crown-6)], resulting in a P21/n space group.

Slow dynamics of electrons at a metal-Mott insulator boundary in an organic system with disorder.

The Mott transition-a metal-insulator transition caused by repulsive Coulomb interactions between electrons-is a central issue in condensed matter physics because it is the mother earth of various attractive phenomena. Outstanding examples are high- (critical temperature) cuprates and manganites exhibiting colossal magnetoresistance. Furthermore, spin liquid states, which are quantum-fluctuation-driven disordered ground states in antiferromagnets, have recently been found in magnetic systems very near the Mott transition.

A Highly Water-Tolerant Magnesium(II) Coordination Polymer Derived from a Flexible Layered Structure.

A two-dimensional (2D) layered Mg(II) coordination polymer (CP) with a high tolerance for H2 O was designed, synthesised, and crystallographically characterised. The synthesis was achieved by the introduction of a flexible 2D layered structure composed of Mg(II) ions and isonicotinate N-oxide ligands. Owing to its high H2 O tolerance, the obtained 2D layered structure has the flexibility to repeatedly adsorb a large amount of H2 O associated with interlayer expansion and enable the removal of H2 O from a H2 O/2-propanol mixed vapour.

High CO /CH Selectivity of a Flexible Copper(II) Porous Coordination Polymer under Humid Conditions.

The development of highly efficient CO separation materials is very important for environmental preservation and energy conservation. Crystalline porous coordination polymers (PCPs)/metal-organic frameworks are one of a number of promising types of porous materials for CO separation because of their controllable pore size, shape and surface function. Simultaneously, the unique structural flexibility of PCPs affords both high CO selectivity and inexpensive regeneration.

High CO /CH Selectivity of a Flexible Copper(II) Porous Coordination Polymer under Humid Conditions.

Invited for this month's cover is the group of Prof. Shin-ichiro Noro from Hokkaido University, Japan. The cover picture shows a copper(II) porous coordination polymer that can adsorb CO over CH at high selectivity under CO /CH mixed gas conditions, even with the coexistence of water.

Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand.

The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions.

Skeletal muscle loss is negatively associated with single-pool Kt/V and dialysis duration in hemodialysis patients.

We evaluated the skeletal muscle loss in hemodialysis (HD) patients by bioelectrical impedance analysis (BIA) and handgrip strength test. Thirty-four HD patients and 16 healthy subjects (control group) were measured for skeletal muscle mass normalized as the skeletal muscle mass index (SMI), calculated as skeletal muscle mass (kg)/height (m)(2) using a tetrapolar bioelectrical impedance plethysmograph. Handgrip strength test was also performed using a hand dynamometer in both groups.

Positive association of vigorous and moderate physical activity volumes with skeletal muscle mass but not bone density or metabolism markers in hemodialysis patients.

Purpose: To determine whether vigorous and moderate physical activity volumes are associated with skeletal muscle loss and chronic kidney disease-mineral and bone disorder (CKD-MBD) in hemodialysis (HD) patients.

Methods: Skeletal muscle index (SMI) was measured using a bioelectrical impedance plethysmograph, and grip strength using a hand dynamometer, in 32 HD patients and 16 healthy controls. In HD patients, bone density was measured using digital image processing, and serum bone metabolism markers were measured as surrogate markers for CKD-MBD.

Molecule-displacive ferroelectricity in organic supramolecular solids.

Ferroelectricity is essential to many forms of current technology, ranging from sensors and actuators to optical or memory devices. In this circumstance, organic ferroelectrics are of particular importance because of their potential application in tomorrow's organic devices, and several pure organic ferroelectrics have been recently developed. However, some problems, such as current leakage and/or low working frequencies, make their application prospects especially for ferroelectric memory (FeRAM) not clear.

Anion-dependent host-guest properties of porous assemblies of coordination complexes (PACs), [Cu(A)₂(py)₄] (A = PF₆, BF₄, CF₃SO₃, and CH₃SO₃; py = pyridine), based on Werner-type copper(II) complexes in the solid state.

We report the syntheses and crystal structures of novel porous assemblies of coordination complexes (PACs) with/without guest molecules, α-[Cu(A)₂(py)₄] (α-PAC-2-A (A = PF₆, BF₄, CF₃SO₃, and CH₃SO₃); py = pyridine), γ-{[Cu(PF₆)₂(py)₄]·2guest} (γ-PAC-2-PF₆ ⊃ 2guest (guest = acetone and py)), γ-{[Cu(BF₄)₂(py)₄]·2acetone} (γ-PAC-2-BF₄ ⊃ 2acetone), and β-{[Cu(CH₃SO₃)₂(py)₄]·2.67H₂O} (β-PAC-2-CH₃SO₃ ⊃ 2.67H₂O).

Rational synthesis of a porous copper(II) coordination polymer bridged by weak Lewis-base inorganic monoanions using an anion-mixing method.

The use of divalent Cu(II) ions and an anion-mixing method led to the rational construction of a porous coordination polymer bridged by weak Lewis-base inorganic CF3SO3(-) monoanions.

Porous coordination polymer polymorphs with different flexible pores using a structurally flexible and bent 1,3-bis(4-pyridyl)propane ligand.

Porous coordination polymer (PCP) polymorphs with the formula [Cu(CF3SO3)2(bpp)2]n [1 and 2, where bpp = 1,3-bis(4-pyridyl)propane] have been synthesized and crystallographically characterized, and their distinguishable porous properties have been investigated. 1 was obtained by the removal of guest acetone molecules from one-dimensional PCP {[Cu(CF3SO3)(bpp)2]·CF3SO3·2acetone}n (1⊃2acetone), while 2 was derived from two-dimensional PCP {[Cu(CF3SO3)2(bpp)2]·H2O}n (2⊃H2O) by the loss of guest H2O molecules. The desolvated PCPs 1 and 2 with the same formula [Cu(CF3SO3)2(bpp)2] showed distinguishable structures, suggesting PCP polymorphs.

Molecular motion in pyridazinium/crown ether supramolecular cation salts of a nickel dithiolene complex.

Supramolecular cations formed by monoprotonated pyridazinium cations and cis-anti-cis-dicyclohexano[18]-crown-6 (DCH[18]-crown-6) or dibenzo[18]-crown-6 (DB[18]-crown-6) were introduced into [Ni(dmit)2]− salts (where dmit2− = 2-thione-1,3-dithiole-4,5-dithiolate). X-ray crystal structure analysis of (pyridazinium+)(DCH[18]-crown-6)[Ni(dmit)2]− (1) revealed a chair-type conformation of the DCH[18]-crown-6 moiety. A V-shaped conformation of the DB[18]-crown-6 moiety was observed in (pyridazinium+)(DB[18]-crown-6)2[Ni(dmit)2]−(H2O)2 (2).

New BDH-TTP/[M(III)(C5O5)3]3- (M = Fe, Ga) isostructural molecular metals.

Two new isostructural molecular metals-(BDH-TTP)(6)[M(III)(C(5)O(5))(3)]·CH(2)Cl(2) (BDH-TTP = 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene, where M = Fe (1) and Ga (2))-have been prepared and fully characterized. Compound 1 is a molecular conductor showing paramagnetic behavior, which is due to the presence of isolated [Fe(C(5)O(5))(3)](3-) complexes with high-spin S = (5)/(2) Fe(III) metal ions. The conductivity originates from the BDH-TTP organic donors arranged in a κ-type molecular packing.

Supramolecular rotators of (aniliniums)([18]crown-6) in electrically conducting [Ni(dmit)2] crystals.

Supramolecular assemblies of anilinium (Ani(+)) and fluoroanilinium derivatives (FAni(+)) with [18]crown-6 were introduced into electrically conducting [Ni(dmit)(2)] crystals (dmit(2-) is 2-thioxo-1,3-dithiole-4,5-dithiolate). The crystal structures, electrical conductivities, and magnetic susceptibilities of four new crystals of (Ani(+))([18]crown-6)[Ni(dmit)(2)](3) (1), (o-FAni(+))([18]crown-6)[Ni(dmit)(2)](3) (2), (m-FAni(+))([18]crown-6)[Ni(dmit)(2)](3) (3), and (p-FAni(+))([18]crown-6)[Ni(dmit)(2)](3) (4) were examined from the viewpoint of dynamic supramolecular rotator structures within the crystals. The crystal structures, electrical conduction, and magnetic properties were classified into group-I (crystals 1 and 4) and group-II (crystals 2 and 3).

Crystal structures and magnetic properties of (4,4'-phenylazophenyl)diammonium(crown ethers)[Ni(dmit)2]2 crystals.

Sandwich-type hydrogen-bonded supramolecular dications (DAAz(2+))([18]crown-6)(2) and (DAAz(2+))(dicyclohexane[18]crown-6)(2) (DAAz(2+) = 4,4'-(phenylazophenyl)diammonium) were introduced into [Ni(dmit)(2)](-) anions via a diffusion method to form novel single crystals (DAAz(2+))([18]crown-6)(2)[Ni(dmit)(2)](2) (1) and (DAAz(2+))(dicyclohexane[18]crown-6)(2)[Ni(dmit)(2)](2) (2), respectively, which were characterized based on their crystal structures and magnetic susceptibilities. The molecular assembly structures and its physical properties were expanded in the use of a three component molecular network system. The two ammonium groups (-NH(3)(+)) of the DAAz(2+) dication formed N-H(+)-O hydrogen-bonding interactions with the oxygen atoms of [18]crown-6 and dicyclohexane[18]crown-6.

Electronic state of a conducting single molecule magnet based on Mn-salen type and Ni-dithiolene complexes.

The electrochemical oxidation of an acetone solution containing [Mn(III) (5-MeOsaltmen)(H(2)O)](2)(PF(6))(2) (5-MeOsaltmen(2-) = N,N'-(1,1,2,2-tetramethylethylene)bis(5-methoxysalicylideneiminate)) and (NBu(4))[Ni(dmit)(2)] (dmit(2-) = 2-thioxo-1,3-dithiole-4,5-dithiolate) afforded a hybrid material, [Mn(5-MeOsaltmen)(acetone)](2)[Ni(dmit)(2)](6) (1), in which [Mn(2)](2+) single-molecule magnets (SMMs) with an S(T) = 4 ground state and [Ni(dmit)(2)](n-) molecules in a charge-ordered state (n = 0 or 1) are assembled in a layer-by-layer structure. Compound 1 crystallizes in the triclinic space group P1 with an inversion center at the midpoint of the Mn···Mn dimer. The [Mn(2)](2+) unit has a typical nonplanar Mn(III) dimeric core and is structurally consistent with previously reported [Mn(2)] SMMs.

Paramagnetic-diamagnetic phase transition accompanied by coordination bond formation-dissociation in the dithiolate complex Na[Ni(pdt)2]·2H2O.

Bis(2,3-pyrazinedithiolate)nickel complex Na[Ni(pdt)(2)]·2H(2)O formed one-dimensional stacks of the Ni(pdt)(2) units and showed strong antiferromagnetic interactions along the stacking direction. A first-order phase transition between the paramagnetic and diamagnetic states, which was driven by dimerization of the Ni(pdt)(2) units, accompanied by coordination bond formation, was observed.

Magnetic/conducting bifunctionality due to π/σ-conjugated functional moieties in a stacked ferrimagnetic chain.

An alternating chain of a paddlewheel [Ru(2)(II,III)(O(2)CEt)(4)](+) (EtCO(2)(-) = propionate) complex and [Pt(mnt)(2)](-) (mnt(2-) = maleonitriledithiolate) has a ferrimagnetic spin arrangement of S = 3/2 and 1/2 local spins, respectively, as well as three-dimensional antiferromagnetic ordering with a canting mode at 8.6 K. This chain is stacked at the [Pt(mnt)(2)](-) units to form a slipped column in the vertical direction against the chain, which acts as a pathway for electrical conduction.

Electrical properties and electronic states of molecular conductors based on unsymmetrical organometallic-dithiolene gold(III) complexes.

The electronic properties of cation radical salts derived from organometallic mixed-ligand complexes [(ppy)Au(S-S)](ppy- = C-dehydro-2-phenylpyridine(-); S-S(2-) = dithiolene ligand) with Au(III)-C sigma-bond were investigated. A 2:1 salt complex [(ppy)Au(C8H4S8)]2[PF6] (C8H4S8(2-) = 2-((4,5-ethylenedithio)-1,3-dithiole-2-ylidene)-1,3-dithiole-4,5-dithiolate(2-)) exhibited semiconductive behavior under ambient pressure (rho rt = 2.6 Omega cm, Ea = 0.

Preparation and characterization of conducting trimetallic nickel-dithiolene complexes with bridging tetrathiooxalate ligands.

Trimetallic nickel dithiolene complexes with two tetrathiooxalate (tto) ligands were obtained by a reaction monitored by ESI-mass spectrometry followed by HPLC separation and were characterized by elemental or crystal structural analysis, MO calculations, and electrical conductivity measurements.