Effect of the Formation of Highly Ordered Platinum(II) Octaethylporphyrin Adlayer on the Surface Reconstruction of Gold and Supramolecular Assembly of Fullerenes

The structures of 2D molecular assemblies of platinum­(II) octa­ethylporphyrin (PtOEP) on Au(111) and Au(100) surfaces were examined using in situ scanning tunneling microscopy (STM) in 0.05 M HClO₄ solutions. The in situ STM observations revealed that the reconstructed rows of Au(111) and Au(100) were stabilized through the formation of highly ordered arrays by adsorption of PtOEP in a wide potential range of the electric double-layer region and that the PtOEP overlayer expanded the stable potential range for the reconstructed phase. Furthermore, the supramolecular assembly of C₆₀ and C₈₄ on a highly ordered PtOEP adlayer formed on Au(111) surfaces was investigated. STM images revealed site-selective supramolecular assembly of fullerenes, especially C₈₄, which exhibited a low coverage on the PtOEP adlayer. C₆₀ molecules exhibited a full coverage and formed highly ordered adlayers on PtOEP, whereas C₈₄ exhibited disordered arrays. The results of this study showed that the strong π-electron donation by the PtOEP molecules stabilized the reconstructed rows of single-crystal Au planes and that the PtOEP adlayer acted as a strong electron-donating layer, aiding the formation of supramolecularly assembled C₆₀ molecules

Two Sharp Phase Change Processes of Diphenyl Viologen at a Au(111) Electrode Surface: Non-Faradaic Transition with Interplay of Ionic Adsorption of Chloride and Bromide and Faradaic One

Two phase change processes of diphenyl viologen (dPhV) on a Au(111) electrode in KCl and KBr aqueous solutions were described using the results of voltammetric, electroreflectance (ER), and electrochemical scanning tunneling microscopic (EC-STM) measurements. Both processes exhibited sharp spikelike voltammetric responses. In KCl solution, the phase change at 0.30 V versus Ag/AgCl/saturated KCl was found to be a nonfaradaic order–disorder phase transition, from an ordered adlayer of dPhV dication (dPhV²⁺) with coadsorbed Cl^– at more positive potentials than 0.30 V to a gaslike phase at less positive potentials. The faradaic reaction at −0.09 V was found to be the transition from the gaslike phase to a condensed monolayer of dPhV^•+. The EC-STM images of the condensed monolayer showed stripe patterns of rows of π–π stacked dPhV^•+. Almost the same set of two processes was observed in KBr solution but not in KF solution. In KF solution, although two voltammetric responses were observed, the peaks were small and broad, indicative of sluggish adsorption state changes of individual dPhV cations. Taken together, specific adsorption of coexistent anions is of critical importance for the occurrence of the sharp nonfaradaic phase transition

Conformational Change in Molecular Assembly of Nickel(II) Tetra(<i>n</i>‑propyl)porphycene Triggered by Potential Manipulation

Metal-coordinated porphyrin and related compounds are important for developing molecular architectures that mimic enzymes. Porphycene, a structural isomer of porphyrin, has shown unique properties in semiartificial myoglobin. To explore its potential as a molecular building block, we studied the molecular assembly of nickel­(II) tetra­(<i>n</i>-propyl)­porphycene (NiTPrPc), a metalloporphycene with introduced tetra <i>n</i>-propyl moieties, on the Au(111) electrode surface using in situ scanning tunneling microscopy. Because of the low molecular symmetry of NiTPrPc, the molecular assembly undergoes unique phase transitions due to conformational change of the <i>n</i>-propyl moieties. The phase transitions can be precisely controlled by the electrode potential, demonstrating that the latter can play an important role in the porphycene molecular assembly on Au surface. This new discovery indicates possible uses of this porphycene framework in molecular engineering

Non-contact laser printing of ag nanowire-based electrode with photodegradable polymers

\u3cp\u3eThe roll-to-roll process is synonymous with newspaper production. If a similar high-throughput process is developed to fabricate electronics over large areas, it would revolutionize the printed electronics manufacturing process. Rapid fabrication of electrode, including patterning and nanoscale welding, is a necessary integration technique to reduce the duration of the process, but faces difficulties in being realized using conventional methods. This paper discusses material factors that affect printability, in the context of developing a promising fabrication technique called laser induced forward transfer (LIFT); LIFT is non-contact printing technique applied previously to realize simultaneous pattern deposition and nanowelding of Ag nanowire (AgNW)-based electrodes. A photodegradable polymer, which is a key component in the printing process to render droplet acceleration, is investigated with regards to its mechanical and optical properties. Furthermore, the printing process of the AgNW-based electrode is visualized, resulting in deeper understanding of LIFT. Knowledge of these factors will contribute to rapid and precise patterning of AgNW-based electrodes with high stretchability and transparency toward flexible optoelectronics devices.\u3c/p\u3

Non-contact laser printing of ag nanowire-based electrode with photodegradable polymers

The roll-to-roll process is synonymous with newspaper production. If a similar high-throughput process is developed to fabricate electronics over large areas, it would revolutionize the printed electronics manufacturing process. Rapid fabrication of electrode, including patterning and nanoscale welding, is a necessary integration technique to reduce the duration of the process, but faces difficulties in being realized using conventional methods. This paper discusses material factors that affect printability, in the context of developing a promising fabrication technique called laser induced forward transfer (LIFT); LIFT is non-contact printing technique applied previously to realize simultaneous pattern deposition and nanowelding of Ag nanowire (AgNW)-based electrodes. A photodegradable polymer, which is a key component in the printing process to render droplet acceleration, is investigated with regards to its mechanical and optical properties. Furthermore, the printing process of the AgNW-based electrode is visualized, resulting in deeper understanding of LIFT. Knowledge of these factors will contribute to rapid and precise patterning of AgNW-based electrodes with high stretchability and transparency toward flexible optoelectronics devices