Ionic channel structures in [(M+)x([18]crown-6)][Ni(dmit)2]2 molecular conductors.

The [(M+)x[18]crown-6)] supramolecular cations (SC+), in which M+ and [18]crown-6 are alkali metal ions (M+ = Li+, Na+, and Cs+) and 1,4,7,10,13,16-hexaoxacyclooctadecane, respectively, form ionic channel structures through the regular stacks of [18]crown-6 in [Ni(dmit)2]-based molecular conductors (dmit2+ = 2-thioxo-1,3-dithiole-4,5-dithiolate). In addition to the [Ni(dmit)2] salts that have the ionic channel structures (these salts are abbreviated as type I salts), Li+ and Na+ form dimerized [(M+)2([18]crown-6)2] units in the crystals (type II salts). The K+ and Rb+ are coordinated tightly into the [18]crown-6 cavity to form typical disk-shape SC+ units in the corresponding [Ni(dmit)2] salts (type III salts). The type I, II, and III salts have typical stoichiometries of [(M+)x([18]crown-6)][Ni(dmit)2]2, [(M+)([18]crown-6)(H2O)x(CH3CN)(1.5 - x)][Ni(dmit)2]3 (x = 1 for Li+ or 0.5 for Na+), and [M+([18]crown-6)][Ni(dmit)2]3, respectively: the salts of the same type are isostructural. In agreement with the trimer structures of [Ni(dmit)2] in the type II and III salts, they exhibit semiconducting behavior with electrical conductivities at 300 K (sigma(300 K)) of 0.01-0.1 S cm(-1). Type I salts contain a regular stack of partially oxidized [Ni(dmit)2] units, which form a quasi one-dimensional metallic band within the tight-binding approximation regime. The electrical conductivities at 300 K are 10-30 S cm(-1), and an almost temperature-independent conductivity was observed at higher temperatures. However, the one-dimensional electronic structures in these salts are strongly influenced by the static and dynamic structures of the coexisting ionic channel. The Na+ salt is a semiconductor, whose magnetic behavior is described by the disordered one-dimensional antiferromagnetic chain. On the other hand, the Cs+ salt is a exhibits metallic properties with 2 kF instability at room temperature. The Li+ salt shows a gradual transition from the high-temperature metallic phase to the low-temperature one-dimensional antiferromagnetic semiconductor phase, which was associated with the freezing of Li+ motion at lower temperatures. The preferential crystallization of type I salts was possible by controlling the equilibrium constant (Kc) of the complex formation between M+ ions and the [18]crown-6 molecule. The ionic channel structures were obtained when the KC was low in the electrocrystallization solution, while type II or III salts were formed in the high Kc region.

M+(12-crown-4) supramolecular cations (M+ = Na+, K+, Rb+, and NH4+) within Ni(2-thioxo-1,3-dithiole-4,5-dithiolate)2 molecular conductor.

Monovalent cations (M+ = Na+, K+, Rb+, and NH4+) and 12-crown-4 were assembled to new supramolecular cation (SC+) structures of the M+(12-crown-4)n (n = 1 and 2), which were incorporated into the electrically conducting Ni(dmit)2 salts (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate). The Na+, K+, and Rb+ salts are isostructural with a stoichiometry of the M+(12-crown-4)2[Ni(dmit)2]4, while the NH4+ salt has a stoichiometry of NH4+(12-crown-4)[Ni(dmit)2]3(CH3CN)2. The electrical conductivities of the Na+, K+, Rb+, and NH4+ salts at room temperature are 7.87, 4.46, 0.78, and 0.14 S cm-1, respectively, with a semiconducting temperature dependence. The SC+ structures of the Na+, K+, and Rb+ salts have an ion-capturing sandwich-type cavity of M+(12-crown-4)2, in which the M+ ion is coordinated by eight oxygen atoms of the two 12-crown-4 molecules. On the other hand, the NH4+ ion is coordinated by four oxygen atoms of the 12-crown-4 molecule. Judging from the M(+)-O distances, thermal parameters of oxygen atoms, and vibration spectra, the thermal fluctuation of the Na+(12-crown-4)2 structure is larger than those of K+(12-crown-4)2 and Rb+(12-crown-4)2. The SC+ unit with the larger alkali metal cation gave a stress to the Ni(dmit)2 column, and the SC+ structure changed the pi-pi overlap mode and electrically conducting behavior.

Metal complexes of anti-inflammatory drugs. Part VIII: Suprofen complex of copper(II).

The preparation and properties of the copper(II) complex Cu(SUP)2.H2O are reported for the anti-inflammatory drug Suprofen (SUP). The diffuse reflectance spectra and magnetic moment are consistent with a dinuclear structure as found for [Cu(aspirinate)2(H2O)]2. The copper(II) complex exhibits an increased superoxide dismutase activity compared with the parent drug molecule in the nitroblue tetrazolium assay.

Metal complexes of antiinflammatory drugs. Part VII: Salsalate complex of copper(II).

The preparation and properties of the Cu(II) complex Cu(SAS)2.H2O are reported for the antiinflammatory drug Salsalate (SAS). The diffuse reflectance spectra and magnetic moments are consistent with a dinuclear structure as found for [Cu(aspirinate)2(H2O)]2. The Cu(II) complex exhibits an increased superoxide dismutase activity compared with the parent drug molecule in the nitroblue tetrazolium assay.

A new low-dimensional metal, Cs[Pd(S2C2(CN)2)2]·0.5 H2O.

The discovery of a low-temperature superconducting state in organic compounds of the type (TMTSF)2CIO4 (Tc = 1.2 K) and (BEDT-TTF)2AuI2 (TC = 4 K) (where TMTSF is tetramethyltetraselenafulvalene, BEDT-TTF is bis(ethylenedithiolo)tetrathiafalvalene and Tc is the superconducting transition temperature) has stimulated the search for new materials that may show higher values of Tc (refs 1-3). The general problem encountered in molecular charge-transfer salts of this type, which have conduction bands formed by intermolecular overlap of π-electron systems, is that conduction is usually quasi-one-dimensional, with good conduction along the stacking direction. Metals with this one-dimensional character are unstable, and undergo a Peierls transition4 to a semiconducting state at low temperatures. The relatively few exceptions (mentioned above), which remain metallic down to low temperatures, are considered to do so because they show stronger interstack interactions. We report here a new material with inherently two-dimensional interactions between the molecular π-electron systems and which we are able to stabilize as a metal down to low temperatures (1.4 K) under hydrostatic pressure (12 kbar).