Highly selective detection of silver in the low ppt range with ion-selective electrodes based on ionophore-doped fluorous membranes.

Ionophore-doped sensing membranes exhibit greater selectivities and wider measuring ranges if their membrane matrixes are noncoordinating and solvate interfering ions poorly. This is particularly true for fluorous phases, which are the least polar and polarizable condensed phases known. In this work, fluorous membrane matrixes were used to prepare silver ion-selective electrodes (ISEs). Sensing membranes composed of perfluoroperhydrophenanthrene, sodium tetrakis[3,5-bis(perfluorohexyl) phenyl]borate, and one of four fluorophilic Ag(+)-selective ionophores with one or two thioether groups were investigated. All electrodes exhibited Nernstian responses to Ag(+) in a wide range of concentrations. Their selectivities for Ag(+) over interfering ions were found to depend on host preorganization and the length of the -(CH(2))(n)- spacers separating the coordinating thioether group from the strongly electron withdrawing perfluoroalkyl groups. ISEs based on the most selective of the four ionophores, that is, 1,3-bis(perfluorodecylethylthiomethyl)benzene, provided much higher selectivities for Ag(+) over many alkaline and heavy metal ions than most Ag(+) ISEs reported in the literature (e.g., log K(Ag,J)(pot) for K(+), -11.6; Pb(2+), -10.2; Cu(2+), -13.0; Cd(2+), -13.2). Moreover, the use of this ionophore with a linear perfluorooligoether as membrane matrix and solid contacts consisting of three-dimensionally ordered macroporous (3DOM) carbon resulted in a detection limit for Ag(+) of 4.1 ppt (3.8 × 10(-1)1 M).

Dramatic solid-state humidity-induced modification of the magnetic coupling in a dimeric fluorous copper(II)-carboxylate complex.

The very fast and efficient water vapor absorption of the dimeric fluorous copper(II)-carboxylate complex [Cu(2)(C(8)F(17)CO(2))(4)(acetone)(2)] (1) leads, in the solid state, to a dramatic decrease of the exchange magnetic coupling between the copper(II) ions and to a drastic change of its powder EPR spectrum.

Emergent Properties of an Organic Semiconductor Driven by its Molecular Chirality.

Chiral molecules exist as pairs of nonsuperimposable mirror images; a fundamental symmetry property vastly underexplored in organic electronic devices. Here, we show that organic field-effect transistors (OFETs) made from the helically chiral molecule 1-aza[6]helicene can display up to an 80-fold difference in hole mobility, together with differences in thin-film photophysics and morphology, solely depending on whether a single handedness or a 1:1 mixture of left- and right-handed molecules is employed under analogous fabrication conditions. As the molecular properties of either mirror image isomer are identical, these changes must be a result of the different bulk packing induced by chiral composition. Such underlying structures are investigated using crystal structure prediction, a computational methodology rarely applied to molecular materials, and linked to the difference in charge transport. These results illustrate that chirality may be used as a key tuning parameter in future device applications.

Fluorous phase-transfer activation of catalysts: application of a new rate-enhancement strategy to alkene metathesis.

Reactions of the bis(pyridine) complex (H2IMes)(Py)2(Cl)2Ru(=CHPh) and fluorous phosphines P(CH2CH2R(fn))3 (n = a, 6; b, 8; c, 10; R(fn) = (CF2)(n-1)CF3) give (H2IMes)(P(CH2CH2R(fn))3)(Cl)2Ru(=CHPh) (2a-c, 64-73%), which are analogs of Grubbs' second generation catalyst and effective alkene metathesis catalysts under organic monophasic and fluorous/organic biphasic conditions. The latter give rate accelerations, which are believed to arise from phase transfer of the dissociated fluorous phosphine.

A scalable and expedient route to 1-aza[6]helicene derivatives and its subsequent application to a chiral-relay asymmetric strategy.

A rapid route to diversely functionalized 1-aza[6]helicenes has been achieved via the development of a copper-mediated cross-coupling reaction, followed by PtCl4-catalyzed cycloisomerization. Not only does this method allow access to these functionally important molecules on gram scale, but this strategy is also suitable for relaying the axial chirality of a key intermediate to the helicity of the product.

Reversible hydrocarbon/perfluorocarbon phase-switching of [Ru(bipy)3]2+ driven by supramolecular heteromeric fluorous carboxylate-carboxylic acid H-bond interactions.

The Ru(bipy)(3) dication is efficiently and reversibly transferred into perfluorocarbons due to the formation of a highly fluorophillic hydrogen-bonded fluorous carboxylate-carboxylic acid counter-anion, whilst retaining key luminescence and photosensitizer characteristics, for example in singlet oxygen production.

Self-adaptive hydrophilic and coordinating Teflon surfaces through a straightforward physisorption process.

Teflon surfaces exhibiting self-adaptive behaviour with both highly hydrophilic character and strong coordinating properties are prepared in a straightforward manner by physisorption of the fluorophilic copper(II)-carboxylate complex 2.