The Radical Anion of Cyclopentasilane‐Fused Hexasilabenzvalene

The radical anion of cyclopentasilane‐fused hexasilabenzvalene was synthesized by the reduction of the corresponding neutral compound. X‐ray crystallographic analysis showed a more trans‐bent structure of the disilene moiety than the neutral compound. Theoretical calculations showed that the highly trans‐bent structure is attributed to the hexasilabenzvalene structure. The EPR spectrum showed that an unpaired electron exists mainly at the disilene moiety. In the UV/Vis spectrum, a large bathochromic shift was observed compared with the neutral compound.     

Synthesis of GaN nanocrystallites by pulsed laser ablation in pure nitrogen background gases

GaN is a promising material not only for electronic devices but also for photocatalysts. Synthesis of GaN nanocrystal is a key issue to improve performance for these applications. In the present study, GaN nanocrystallites have been synthesized by pulsed laser ablation (PLA), where safe and inactive pure N₂ gases were used as reactive background gases. The third harmonics beam of a Q-switched Nd:YAG laser (355 nm, 10 mJ/pulse, 4 J/(cm² pulse)) was used to ablate a sintered high purity GaN target. The deposition substrates were not heated. It was clarified that the formed GaN nanoparticles contained a hexagonal system with the wurtzite structure. The diameter of the nanocrystallites was about 10 nm, and showed only little dependence on the background gas pressure, while the porosity of the assembly of nanocrystallites and content of GaN nanocrystallites in the assembly increased with background gas pressure. Highly porous nanometer-sized GaN film obtained at higher gas pressure is considered to be candidate structures for the photocatalysts.     

Large-Scale Production of CdSe Nanocrystal by a Continuous Flow Reactor

Organically capped CdSe nanocrystals were successfully produced by a continuous flow reactor in 13 g/h rate as isolated CdSe nanocrystal, using trioctylphosphine oxide (TOPO) both as the capping organic reagent and the high-temperature reaction solvent. Relatively high reaction temperature (e.g. 350°C) was necessary for matured crystal growth. The quality of TOPO (i.e. impurity composition such like phosphonic acids) was also influential on the quality of the resulting CdSe nanocrystal. The continuous flow reactor was able to produce highly-luminescence, monodispersed CdSe nanocrystals, confirmed by transmission electron microscope observation. The production rate was stable at least 1 h to allow over 10 g production.     

Kinetic Control over Pathway Complexity in Supramolecular Polymerization through Modulating the Energy Landscape by Rational Molecular Design

Far‐from‐equilibrium thermodynamic systems that are established as a consequence of coupled equilibria are the origin of the complex behavior of biological systems. Therefore, research in supramolecular chemistry has recently been shifting emphasis from a thermodynamic standpoint to a kinetic one; however, control over the complex kinetic processes is still in its infancy. Herein, we report our attempt to control the time evolution of supramolecular assembly in a process in which the supramolecular assembly transforms from a J‐aggregate to an H‐aggregate over time. The transformation proceeds through a delicate interplay of these two aggregation pathways. We have succeeded in modulating the energy landscape of the respective aggregates by a rational molecular design. On the basis of this understanding of the energy landscape, programming of the time evolution was achieved through adjusting the balance between the coupled equilibria.