Crystallinity-dependence of ionic conductivity in the ion pairs of a multi-interactive anion

Ammonium and sodium salts (ion pairs) of a multi-interactive tri-(4-pyridyl) hexaazaphenalenyl anion (TPHAP(-)) showed completely different ion-conductive properties depending on the crystal structure. TPHAP columnar crystals showed a high conductivity of 10(-3) S cm(-1) while retaining their structures even under humid conditions, whereas TPHAP dimer crystals exhibited a conductivity of similar to 10(-5) S cm(-1) with crystallinity deterioration. The main unit structures induced by multi-interactivity realized different water accessibility, which explains the differences in their ion conductivity and stability against humidity.open1131sciescopu

Crystal surface mediated structure transformation of a kinetic framework composed of multi-interactive ligand TPHAP and Co(II)

A tripyridyl multi-interactive ligand TPHAP is prepared by a one-pot reaction on a gram scale. Network formation of Co(II) with TPHAP(-) gave kinetic and thermally more stable products. The kinetic network showed an unprecedented dynamic network transformation on the crystal surface by a ligand exchange reaction.open111013sciescopu

Selective Formation of Conductive Network by Radical-Induced Oxidation

Cd-based coordination networks having channels were formed selectively by using a redox-active aromatic ligand 2,5,8-tri(4-pyridyl)1,3-diazaphenalene (TPDAP, H+1-). An electron-conductive network having a π-π stacking columnar structure of TPDAP formed in the presence of a trace amount of TPDAP radical (1•). In contrast, a nonconductive network having a dimer unit of H+1- formed in the absence of 1•. These results suggest the presence of a unique oxidation mechanism of TPDAP induced by formation of H+1--1• dimer, which was initiated by a trace amount of 1•. The dimerization increased HOMO level of H+1- moiety within the dimer to generate further radicals that could not form when H+1- was well isolated in CH3OH. © 2016 American Chemical Society1991sciescopu

Selective Formation of Conductive Network by Radical-Induced Oxidation

Cd-based coordination networks having channels were formed selectively by using a redox-active aromatic ligand 2,5,8-tri(4-pyridyl)1,3-diazaphenalene (TPDAP, H(+)1(-)). An electron-conductive network having a pi-pi stacking columnar structure of TPDAP formed in the presence of a trace amount of TPDAP radical (1(center dot)). In contrast, a nonconductive network having a dimer unit of H(+)1(-) formed in the absence of 1(center dot). These results suggest the presence of a unique oxidation mechanism of TPDAP induced by formation of H(+)1(-)-1(center dot) dimer, which was initiated by a trace amount of 1(center dot). The dimerization increased HOMO level of H(+)1(-) moiety within the dimer to generate further radicals that could not form when H(+)1(-) was well isolated in CH3OH.1197sciescopu

Mechanistic Study in Gold Nanoparticle Synthesis through Microchip Laser Ablation in Organic Solvents

The utilization of pulsed laser ablation in liquids (PLALs) for preparing gold nanoparticles (Au NPs) in organic solvents holds immense potential across diverse applications. This study introduces a compact and low-power microchip laser (MCL) system (average power 50 mW; pulse energy 0.5 mJ). Due to its compactness, an MCL is advantageous for easy manipulation in organic laboratories during the production of metal nanoparticles (NPs) for research and development purposes. In this research, poly(N-vinyl-2-pyrrolidone) (PVP) is used as a stabilizing agent for the preparation of Au NPs in organic solvents (CH2Cl2, CHCl3, 2-PrOH, MeCN, DMF, EtOH, NMP, and DMSO). Our experimental results demonstrate that the particle size remains consistent across all the organic solvents. This study explores the productivity of Au NPs in different organic solvents, revealing the necessity of multiple laser pulses to generate Au NPs successfully. This phenomenon, known as the ‘incubation effect,’ is linked to the lower pulse energy in the experimental condition and the thermal conductivity of the solvents. The findings emphasize the crucial role of solvent properties in determining the Au NPs productivity in PLAL

The diversity of Zn(II) coordination networks composed of multi-interactive ligand TPHAP(-) via weak intermolecular interaction

Kinetic state networks can be trapped by multi-interactive ligands via weak intermolecular interactions. Self-assembly of a tripyridyl multi-interactive ligand K+ TPHAP(-) (potassium 2,5,8-tri(4'-pyridyl)-1,3,4,6,7,9-hexaazaphenalene) and ZnI2 produced seven types of networks depending on the solvent systems (MeOH/additive solvent): [ZnI(TPHAP)]center dot 3.5CH(3)OH (1) (from MeOH/DMA), [ZnCl0.5I0.5(TPHAP)H2O]center dot 7H(2)O (2) (from MeOH/DMA + water), [ZnI(TPHAP)]center dot 3PhOH center dot 2CH(3)OH (3) (from MeOH/phenol ( 50%)), [ZnI(TPHAP)]center dot 2PhNO(2)center dot 6CH(3)OH (from MeOH/nitrobenzene) (5), [ZnI(TPHAP)CH3OH] 3PhNH(2) (6) (from MeOH/aniline), and [(ZnI)(2)(TPHAP)(HCON(CH3)(2))(3)(CH3OH)2](+)[(ZnI2)(2)(TPHAP)(HCON(CH3)(2))]- (HCON(CH3)(2))center dot 4CH(3)OH (7) (from MeOH/DMF). All structures were characterized by single crystal X-ray structure determination. Each topology was analyzed by TOPOS. The structures were categorized into two-or three-periodic structure. The structural features of each network were explained by the weak intermolecular interactions between TPHAP(-) and guest molecules. We demonstrated the multi-interactivity of TPHAP(-) which can recognize slight differences of the weak intermolecular interactions.open1158sciescopu