Dynamics of Poly(3-hexylthiophene) Monolayers at Solution/Graphite Interfaces.

We have studied the dynamics of poly(3-hexylthiophene) (P3HT) monolayers at the interfaces between highly oriented pyrolytic graphite (HOPG) and P3HT solutions in 1,2,4-trichlorobenzene, using scanning tunneling microscopy (STM). Real-time STM observation at room temperature reveals that P3HT molecules adsorbed on graphite are substantially mobile even in densely packed conditions, causing significant fluctuations of the self-organized monolayer of P3HT. We find that in the monolayers, the orientational order is limited to a short range comparable to the polymer chain length.

Impact of the Air Atmosphere on Photoinduced Chain Polymerization in Self-Assembled Monolayers of Diacetylene on Graphite.

We have studied the effect of the reaction environment on the photoinduced chain polymerization in self-assembled monolayers of a diacetylene compound 10,12-pentacosadiyn-1-ol on graphite, using scanning tunneling microscopy. Comparing the polymerization behaviors in air and in vacuum, we show that the polymer generation efficiency is considerably enhanced under vacuum because of suppressed collisional quenching of the photoexcited radicals by oxygen molecules. We also find that the polymer chain length tends to increase in vacuum as a result of the inhibition of deactivation of reactive species for the polymer chain growth due to oxidation.

Mechanism of Chain Polymerization in Self-Assembled Monolayers of Diacetylene on the Graphite Surface.

We have studied the mechanism of photoinduced chain polymerization in the self-assembled monolayer of a diacetylene compound, 10,12-pentacosadiyn-1-ol, on the graphite surface. We statistically analyze the polymerization degree of the polydiacetylene chains formed at different temperatures using scanning tunneling microscopy. The distributions of the polymerization degree agree well with the prediction from a simple probabilistic model, allowing for addition reaction and deactivation at both the ends of the chain as stochastic events.

Preparation of Peapod Polymer via the Supramolecular Chain Formation by Tris(spiroborate) Twin Bowl.

Successive guest-containing tubular polymer was prepared by the olefin metathesis polymerization of tris(spiroborate) twin bowl after the formation of supramolecular polymer. The cationic iridium(III) complexes were topologically fixed inside the polymer to form a peapod-like structure. The polymer was evaluated by SEC, ICP-AES, and DLS analyses, and string-like structures were found in the AFM observation of the peapod polymer.

Two-dimensional solid-state topochemical reactions of 10,12-pentacosadiyn-1-ol adsorbed on graphite.

The photoinduced topochemical reaction of the diacetylene (DA) compound 10,12-pentacosadiyn-1-ol in the two-dimensional (2D) crystal phase adsorbed on graphite was examined by scanning tunneling microscopy (STM). The reaction efficiency and the structure of the generated polydiacetylene depend on its polymorphic forms, i.e.

Molecular fluorescence from H2TBP porphyrin film on Ag substrate excited by tunneling electrons.

Molecular fluorescence from H(2)TBP porphyrin (H(2)TBPP) films on Ag substrate is excited by a scanning tunneling microscope (STM) at ambient conditions. The molecular films are prepared by spin-casting method. The thickness of films can be controlled by the times of dropping H(2)TBPP solution.