From an S(T) = 3 single-molecule magnet to diamagnetic ground state depending on the molecular packing of Mn(III)salen-type dimers decorated by N,N'-dicyano-1,4-naphthoquinonediiminate radicals

Two manganese(III) tetradentate Schiff-base dimers to which N,N'-dicyano-1,4-naphthoquinonediiminate (DCNNQI) radicals are attached have been selectively synthesized by varying the solvents used in the reactions: [Mn2(5-MeOsaltmen)2(DCNNQI)2].MeOH (1) and [Mn2(5-MeOsaltmen)(2)(DCNNQI)(2)] x 2CH2Cl2.2CH3CN (2) [5-MeOsaltmen2- = N,N'-(1,1,2,2-tetramethylethylene)bis(5-methoxysalicylideneiminate)]. These two complexes share the same molecular core, [(DCNNQI.-)-Mn(III)-(O)2-Mn(III)-(DCNNQI.-)], where -(O)2- is a biphenolate bridge in the out-of-plane dimerized [Mn(2)(5-MeOsaltmen)2]2+ moiety. However, their packing arrangements are completely different. Whereas complex 1 is found to be relatively isolated, strong intermolecular dimerization of the DCNNQI moieties (with the nearest contact being approximately 3.0 A) is observed in 2, forming a one-dimensional chain of [-Mn(III)-(O)2-Mn(III)-(DCNNQI.-)2-](infinity). The magnetic susceptibility of 1 can be modeled with an [S = 1/2, 2, 2, 1/2] four-spin system including strong antiferromagnetic Mn(III)/DCNNQI radical coupling (J(Mn/rad)/kB = -23 K) and ferromagnetic Mn(III)/Mn(III) coupling through the biphenolate bridge (J(Mn/Mn)/kB = +2.0 K). These interactions lead to an ST = 3 ground state that possesses significant uniaxial anisotropy (D(S=3)/kB = -2.1 K). Low-temperature ac and dc magnetic data of 1 reveal its single-molecule magnet behavior with quantum tunneling of the magnetization. By contrast, 2 possesses the diamagnetic ground state induced by dominating Mn(III)-Mn(III) antiferromagnetic interactions mediated by the diamagnetic DCNNQI dimers and/or pi-pi contact along the b axis.     

Roles of sigmatropic migration of a benzoyl group and intermolecular hydrogen bonding between a tropone carbonyl and an NH group on the mesomorphic properties of 2-(4-alkoxybenzoyloxy)-5-alkylaminotropones and 5-alkoxy-2-(4-alkylaminobenzoyloxy)tropo

The mesomorphic properties of 2-(4-alkoxybenzoyloxy)-5-alkylaminotropones and 5-alkoxy-2-(4-alkylaminobenzoyloxy)tropones are discussed on the basis of results obtained by X-ray crystallographic and X-ray diffraction studies, as well as temperature-dependent FTIR spectral measurements. The X-ray crystallographic analysis of 2-(4-dodecylaminobenzoyloxy)-5-tetradecyloxytropone (2f) indicated that it formed a head-to-tail dimer through an intermolecular hydrogen bond between the NH and the tropone carbonyl group. The X-ray diffraction study of compound 2f suggested that the molecules formed interdigitated bilayer smectic C phases with a tilt angle of as much as c. 40° to a layer plane. The corresponding benzenoids, however, were non-mesomorphic, with higher melting points than the troponoids. In the troponoids, sigmatropic migration of the benzoyl group weakened the intermolecular hydrogen bonding and assisted the occurrence of mesomorphic properties.     

Associative desorption of adsorbed oxygen promoted by translational energy of incident O2 molecules

Effects of the translational energy of incident oxygen molecules on surface processes from dissociative adsorption to subsequent associative desorption on Pt(1 1 1) have been investigated by means of supersonic molecular beam scattering. The reaction rate of associative desorption increases with the incident translational energy. The enhanced associative desorption can be attributed to nonthermal diffusion of dissociated oxygen, promoted by the translational energy of incoming molecules.     

Imaging Analysis of Near-Field Recording Technique for Observation of Biological Specimens

We present an analysis of the properties of an imaging based on a near-field recording technique in comparison with simulation results. In the system, the optical field distributions localized near the specimens are recorded as the surface topographic distributions of a photosensitive film. It is possible to observe both soft and moving specimens, because the system does not require a scanning probe to obtain the observed image. The imaging properties are evaluated using fine structures of paramecium, and we demonstrate that it is possible to observe minute differences of refractive indices.     

Palladium-Catalyzed Cascade Process Consisting of Isocyanide Insertion and Benzylic C(sp(3))-H Activation: Concise Synthesis of Indole Derivatives

Synthesis of the indole skeleton was achieved using a Pd-catalyzed cascade process consisting of isocyanide insertion and benzylic C(sp(3))-H activation. It was found that slow addition of isocyanide is effective for reducing the amount of catalyst needed and Ad(2)P(n)Bu is a good ligand for C(sp(3))-H activation. The construction of the tetracyclic carbazole skeleton was also achieved by a Pd-catalyzed domino reaction incorporating alkyne insertion.     

Trajectory of the spectral/structural rearrangements for photo-oxidative reaction of neat ketoprofen and its cyclodextrin complex

Journal of Inclusion Phenomena and Macrocyclic Chemistry - Ketoprofen is a nonsteroidal anti-inflammatory drug used as mohrus tape which causes unwanted photosensitivity due to UV irradiation. In...     

Electrical conducting bis(oxalato)platinate complex with direct connection of CuII ions

Reactions of K1.62[Pt(ox)2].2H2O and [Cu(bpy)(H2O)3](NO3)2 yielded partially oxidized one-dimensional (1D) bis(oxalato)platinates of [Cu(bpy)(H2O)n]6[Pt(ox)2]7.7H2O (n = 2, 3, or 4) (1) and [Cu(bpy)(H2O)n]8[Pt(ox)2]10.8H2O (n = 3 or 4) (2). The average oxidation numbers of the platinum ions in 1 and 2 are +2.29 and +2.40, respectively. Complexes 1 and 2 crystallize in the triclinic P and monoclinic C2/c space groups, respectively, and the [Pt(ox)2]n- anions are stacked along the crystallographic b axis with 7-fold periodicity for 1 and 10-fold periodicity for 2. In 1, an oxalato ligand in the platinum chain directly coordinates to a paramagnetic [Cu(bpy)(H2O)3]2+ ion, whereas no such direct coordination was observed for 2. The electrical conductivity of 2 at room temperature along the platinum chain is approximately 3 orders of magnitude smaller (sigma||= 1.3 x 10(-3) S cm(-1)) than that of 1 (sigma|| = 0.9-0.5 S cm(-1)), and the activation energies of 1 and 2 are 29 and 67 meV, respectively. The longest inter-platinum distances in 1 and 2 are 2.762 and 3.0082 A, respectively, and this is responsible for the lower electrical conductivity of 2. An X-ray oscillation photograph taken along the b axis of 1 reveals the 7-fold periodicity in the 1D chain, consistent with the period of the Peierls distortion estimated from the degree of partial oxidation. The semiconducting state of 1 can therefore be regarded as a commensurate Peierls state. The magnetoresistance of 1 at ambient pressure indicates no interaction between conduction electrons in the platinum chain and local spins of the paramagnetic CuII ions. Application of hydrostatic pressures of up to 3 GPa enhances electrical conduction, as is often seen as the usual pressure effect on the electrical conductivity, which is due to enhanced orbital (Pt-5dz2) overlap by pressure application.     

Rotational dynamics of water and benzene controlled by anion field in ionic liquids: 1-butyl-3-methylimidazolium chloride and hexafluorophosphate

The rotational correlation time (tau(2R)) is determined for D(2)O (polar) and C(6)D(6) (apolar) in 1-butyl-3-methylimidazolium chloride ([bmim][Cl]) and hexafluorophosphate ([bmim][PF(6)]) by measuring (2)H (D) nuclear magnetic resonance spin-lattice relaxation time (T(1)) in the temperature range from -20 to 110 degrees C. The tau(2R) ratio of water to benzene (tau(WB)) was used as a measure of solute-solvent attraction. tau(WB) is 0.73 and 0.52 in [bmim][Cl] and [bmim][PF(6)], respectively, whereas the molecular volume ratio is as small as 0.11. The slowdown of the water dynamics compared to the benzene dynamics in ionic liquids is interpreted by the Coulombic attractive interaction between the polar water molecule and the anion. As for the anion effect, the rotational dynamics of water solvated by Cl(-) is slower than that solvated by PF(6) (-), whereas the rotational dynamics of benzene is similar in the two ionic liquids. This is interpreted as an indication of the stronger solvation by the anion with a larger surface charge density. The slowdown of the water dynamics via Coulombic solvation is actually significant only at water concentrations lower than approximately 9 mol dm(-3) at room temperature, and it is indistinguishable at temperatures above approximately 100 degrees C. The quadrupolar coupling constants determined for D(2)O and C(6)D(6) in the ionic liquids were smaller by a factor of 2-3 than those in the pure liquid state.     

Visualization of penetration of a high-speed focused microjet into gel and animal skin

Journal of Visualization - Realization of a needle-free drug delivery device can solve needle-caused problems. Recently, attention has been given to the use of a focused liquid jet instead of the...