Structural insights into the coordination and extraction of Pb(II) by disulfonamide ligands derived from o-phenylenediamine.

The o-phenylenediamine-derived disulfonamide ligands 1 and 2 complex and efficiently extract Pb(II) from water into 1,2-dichloroethane via ion-exchange, in combination with 2,2'-bipyridine (97.5% and 95.0%, respectively, for 1:1 ligand-to-Pb ratios). The corresponding Pb(II)-sulfonamido binary complexes of ligands 1 and 2 (3 and 4, respectively), and ternary complexes with 2,2'-bipyridine (5 and 6, respectively), were isolated and characterized. (1)H NMR spectra of the organic phases after extraction show the formation of ternary Pb-sulfonamido-bipy complexes. X-ray characterization of 3, 4, and the ternary complex 5 consistently demonstrates four primary coordination sites and a stereochemically active lone pair on Pb. The X-ray structure of 3 shows a pseudo trigonal bipyramidal configuration on Pb, with the lone pair occupying one of the equatorial sites, and the formation of an unusual "hemidirected" coordination polymer via axial S=O-Pb coordination. The same axial S=O-Pb coordination pattern with two DMSO molecules is observed in the structure of 4.[2(CH(3))(2)SO)], thus rationalizing the high solubility of the binary complexes in strongly coordinating solvents. In contrast, the X-ray structure of the ternary complex 5 reveals a distorted four-coordinate configuration with only weak S=O-Pb coordination leading to dimer formation, thus explaining its higher solubility in weakly coordinating solvents. FT-IR spectroscopy confirms the X-ray data, since the ligand nu(S)(=)(O) stretching frequencies shift to lower values in the binary Pb(II)-sulfonamido complexes and are again altered upon formation of the ternary Pb(II)-sulfonamido-bipy complexes, as would be expected for 2,2'-bipy complexation and hindered S=O-Pb coordination.

Self-assembling bipyridinium multilayers.

The identification of strategies to assemble nanostructured films with engineered properties on solid supports can lead to the development of innovative functional materials. In particular, the self-assembly of electroactive multilayers from simple molecular building blocks on metallic electrodes can offer the opportunity to regulate the exchange of electrons between the underlying substrate and solution species. In this context, we designed an experimental protocol to prepare electroactive films from bipyridinium bisthiols. Specifically, we found that a compound incorporating two bipyridinium dications at its core and terminal thiol groups self-assembles into remarkably stable multilayers on polycrystalline gold. The surface coverage of the resulting films can be regulated by adjusting the exposure time of the gold substrate to the bipyridinium solution. Control experiments with appropriate model compounds demonstrate that both bipyridinium dications as well as both thiol groups must be present in the molecular skeleton to encourage multilayer growth. The resulting films transport electrons efficiently from the electrode surface to the film/solution interface. Indeed, they mediate the reduction of Ru(NH(3))(6)(3+) in the electrolyte solution but prevent the back oxidation of the resulting Ru(NH(3))(6)(2+). Furthermore, these polycationic bipyridinium films capture electrostatically Fe(CN)(6)(4-) tetraanions, which can also be exploited to transport electrons across the interfacial assembly. In fact, electrons can travel through the bipyridnium(2+/1+) couples to redox probes in solution and then back to the electrode through the Fe(CN)(6)(4/3-) couples. Thus, our original approach to self-assembling multilayers can produce stable electroactive films with unique electron transport properties, which can be regulated with a careful choice of the anionic components.

Electron transport in bipyridinium films.

Bipyridinium dications are versatile building blocks for the assembly of functional materials. In particular, their reliable electrochemical response has encouraged the design of electroactive films. Diverse and elegant experimental strategies to coat metallic and semiconducting electrodes with bipyridinium compounds have, in fact, emerged over the past two decades. The resulting interfacial assemblies span from a few nanometers to several micrometers in thickness. They incorporate from a single molecular layer to large collections of entangled polymer chains. They transport electrons efficiently from the electrode surface to the film/solution interface and vice versa. Electron self-exchange between and the physical diffusion of the bipyridinium building blocks conspire in defining the charge transport properties of these fascinating electroactive assemblies. Often, the matrix of electron-deficient bipyridinium dications can be exploited to entrap electron-rich analytes. Electrostatic interactions promote the supramolecular association of the guests with the surface-confined host matrix. Furthermore, chromophoric sites can be coupled to the bipyridinium dications to produce photosensitive arrays capable of harvesting light and generating current. Thus, thorough investigations on the fundamental properties of these functional molecule-based materials can lead to promising applications in electroanalysis and solar energy conversion, while contributing to advances in the basic understanding of electron transport in interfacial assemblies.

Memory effects based on intermolecular photoinduced proton transfer.

We have identified a strategy to communicate a chemical signal between two independent molecular components. One of them is a photoactive merocyanine that switches to a spiropyran, releasing a proton, when stimulated with visible light. The other is a 4,4'-pyridylpyridinium monocation that captures the released proton, producing an electroactive 4,4'-bipyridinium dication. Under the irradiation conditions employed, the photoinduced transformation requires ca. 15 min to reach a photostationary state. In the dark, the ensemble of communicating molecules reequilibrates to the original state in ca. 5 days. These processes can be monitored following the photoinduced enhancement and thermal decay, respectively, of the current for the monolectronic reduction of the 4,4'-bipyridinium dication. The pronounced difference in time scale for the current enhancement and decay steps can be exploited to implement a memory element with a bit retention time of 11 h. A bit of information can be written optically in the chemical system and it can be read electrically and nondestructively. The memory can be reset, extending its permanence in the dark beyond the bit retention time. A binary logic analysis of the signal transduction operated by the communicating molecules reveals the characteristic behavior of sequential logic operators, which are the basic components of digital memories.

Stilbazulenyl nitrone (STAZN): a nitronyl-substituted hydrocarbon with the potency of classical phenolic chain-breaking antioxidants.

Stilbazulenyl nitrone (STAZN), 8, a nitronyl-substituted hydrocarbon, is a novel second-generation azulenyl nitrone with significantly enhanced potency as a chain-breaking antioxidant vs conventional alpha-phenyl nitrones previously investigated as antioxidant therapeutics. A convenient (1)H NMR-based assay for assessing the potency of chain-breaking antioxidants has shown that STAZN is ca. 300 times more potent in inhibiting the free radical-mediated aerobic peroxidation of cumene than is PBN and the experimental stroke drug NXY-059. Such levels of antioxidant efficacy are unprecedented among archetypal alpha-phenyl nitrone spin traps. Furthermore, STAZN outperforms such classical phenolic antioxidants as BHT and probucol and rivals the antioxidant potency of Vitamin E in a polar medium comprised of 80% cumene and 20% methanol. The Volodarskii electron-transfer mechanism involving the intermediacy of the STAZN radical cation has been implicated in attempts to ascertain the basis for the increased potency of STAZN over the three alpha-phenyl nitrones PBN, S-PBN, and NXY-059.