Prolongation of the lifetime of the charge-separated state at low temperatures in a photoinduced electron-transfer system of [60]fullerene and ferrocene moieties tethered by rotaxane structures

A rotaxane tethering both fullerene (C60) and ferrocene (Fc) moieties (abbreviated as (C60;Fc)rotax+) was synthesized in a good yield by the urethane end-capping of pseudorotaxane based on the crown ether-secondary amine motif. In (C60;Fc)rotax+, the C60 group serving as an electron acceptor is attached to the crown ether wheel, through which the axle with a Fc group acting as an electron donor on its end penetrates. The intrarotaxane photoinduced energy-transfer and electron-transfer processes between C60 and Fc in (C60;Fc)rotax+ have been investigated by time-resolved transient absorption and fluorescence measurements with changing solvent polarity. Nanosecond transient absorption measurements of the rotaxane demonstrated that the charge-separated state (C60*-;Fc*+)rotax+ is formed mainly via the excited triplet state of C60 in polar solvents. The lifetime of (C60*-;Fc*+)rotax+ was evaluated to be 20 ns in dimethylformamide (DMF) at room temperature. With lowing temperature, the lifetime of (C60*-;Fc*+)rotax+ extends to 270 ns in DMF at -65 degrees C, due to the structural changes leaving C60*- and Fc*+ at a relatively long distance in the low-temperature region.     

Electronic interplay on illuminated aqueous carbon nanohorn-porphyrin ensembles

Tetracationic water-soluble porphyrin (H(2)P(4+)) has been immobilized by pi-pi stacking interactions onto the skeleton of carbon nanohorns (CNH), without disrupting their pi-electronic network. The stable aqueous solution of the CNH-H(2)P(4+) nanoensemble was examined by both electron microscopy and spectroscopic techniques. The efficient fluorescence quenching of the H(2)P(4+) moiety in the CNH-H(2)P(4+) nanoensemble was probed by steady-state as well as time-resolved fluorescence emission spectroscopy, suggesting charge separation from the photoexcited H(2)P(4+) to CNH. In the presence of methyl viologen dication (MV(2+)) and a hole trap, accumulation of the reduced species of methyl viologen was observed by the photoillumination of CNH-H(2)P(4+), suggesting that the electron migration from the initially formed charge-separated state takes place. Transient absorption spectroscopy gave further insights on the transient species such as the charge-separated state (CNH(*-))-(H(2)P(4+))(*+), which was consumed in the presence of MV(2+) and hole shifter, leaving the reduced methyl viologen.     

A photoelectrochemical device with a nanostructured SnO2 electrode modified with composite clusters of porphyrin-modified silica nanoparticle and fullerene

A silica nanoparticle has been successfully employed as a nanoscaffold to self-organize porphyrin and C60 molecules on a nanostructured SnO2 electrode. The quenching of the porphyrin excited singlet state on the silica nanoparticle is suppressed significantly, showing that silica nanoparticles are promising scaffolds for organizing photoactive molecules three-dimensionally in nanometer scale. Marked enhancement of the photocurrent generation was achieved in the present system compared with the reference system, where a gold core was employed as a scaffold of porphyrins instead of a silica nanoparticle. The rather small incident photon-to-current efficiency relative to a similar photoelectrochemical device using a silica microparticle may result from poor electron and hole mobility in the composite film due to poor connection between the composite clusters of a porphyrin-modified silica nanoparticle and C60 in micrometer scale.     

Dynamic and collective electrochemical responses of tetrathiafulvalene derivative self-assembled monolayers

Electroactive tetrathiafulvalene (TTF)-containing alkanethiol self-assembled monolayers (SAMs) were designed and synthesized to elucidate the relationship between electrochemical responses and film structures. Two TTF derivative molecules having one alkanethiol chain (1) and two alkanethiol chains (2) were utilized to modulate the molecular packing arrangements in the SAMs, and the formation and structure of the SAMs were characterized by surface plasmon resonance spectroscopy (SPR). SPR measurements in various contacting media demonstrated loose packing of SAM 1 and close packing of SAM 2 due to the different space fillings of the molecules. Two successive one-electron redox waves were observed for both SAMs by cyclic voltammetry. The peak widths of the redox waves were strongly dependent on the oxidation states of the TTF moieties, the packing arrangement of the SAMs, and the contacting medium. We found that TTF-based SAMs exhibited collective electrochemical responses induced by dynamic structural changes, depending on the degree of freedom for the component molecules in the SAMs. These results imply that the molecular design, taking into account the electrochemical responses, extends the available range of molecular-based functionalities in TTF-based SAMs.     

Thermal hysteresis and thickness dependence of the molecular orientation of poly(di-n-hexylsilane) in the film state

Molecular orientation of poly(di-n-hexylsilane) adsorbed on poly(vinyl alcohol) film has been studied by making use of the stretching technique. Dichroic ratio, Rd, strongly depended on the thickness of poly(di-n-hexylsilane) thin film and the highest value ca. 19 was observed at the film thickness of 110 +/- 30 nm. The thermal hysteresis of the molecular orientation was observed in the heating-cooling cycles. By studying the fluorescence spectrum it was confirmed that a portion of the poly(di-n-hexylsilane) molecules were in transoid conformation even at 320 K, although most of poly(di-n-hexylsilane) molecules were in disordered conformation (conformation D). This poly(di-n-hexylsilane) in transoid conformation is formed in the stretching process and may play a role of crystallization nucleus to induce the whole orientation of the poly(di-n-hexylsilane) in the film state.     

Structure and Classification of Superconformal Nets

We study the general structure of Fermi conformal nets of von Neumann algebras on S ¹ and consider a class of topological representations, the general representations, that we characterize as Neveu–Schwarz or Ramond representations, in particular a Jones index can be associated with each of them. We then consider a supersymmetric general representation associated with a Fermi modular net and give a formula involving the Fredholm index of the supercharge operator and the Jones index. We then consider the net associated with the super-Virasoro algebra and discuss its structure. If the central charge c belongs to the discrete series, this net is modular by the work of F. Xu and we get an example where our setting is verified by taking the Ramond irreducible representation with lowest weight c/24. We classify all the irreducible Fermi extensions of any super-Virasoro net in the discrete series, thus providing a classification of all superconformal nets with central charge less than 3/2. Sebastino Carpi: Supported by MIUR, GNAMPA-INDAM and EU network “Noncommutative Geometry” MRTN-CT-2006-0031962 Yasuyuki Kawahigashi: Supported in part by the Grants-in-Aid for Scientific Research, JSPS. Submitted: March 3, 2008. Accepted: May 5, 2008.