Satoshi Horike

Treatment of selected aldehydes and ketones with cyanotrimethylsilane in the presence of the microporous metal-organic framework Mn3[(Mn4Cl)3BTT8(CH3OH)10]2 (1, H3BTT = 1,3,5-benzenetristetrazol-5-yl) leads to rapid conversion to the corresponding cyanosilylated products. The transformation is catalyzed by coordinatively unsaturated Mn2+ ions that serve as Lewis acids and lead to conversion yields of 98 and 90% for benzaldehyde and 1-naphthaldehyde, the highest thus far for a metal-organic frame

Ion conduction and transport in solids are both interesting and useful and are found in widely distinct materials, from those in battery-related technologies to those in biological systems. Scientists have approached the synthesis of ion-conductive compounds in a variety of ways, in the areas of organic and inorganic chemistry. Recently, based on their ion-conducting behavior, porous coordination polymers (PCPs) and metal-organic frameworks (MOFs) have been recognized for their easy design and t

Design of molecular structures showing fast ion conductive/transport pathways in the solid state has been a significant challenge. The amorphous or glassy phase in organic polymers works well for fast ion conductivity because of their dynamic and random structure. However, the main issue with these polymers has been the difficulty in elucidating the mechanisms of ion conduction and thus low designability. Furthermore, the amorphous or glassy state of ion conductive polymers often confronts the p

The development of anhydrous proton-conducting materials is critical for the fabrication of high-temperature (>100 °C) polymer electrolyte membrane fuel cells (HT-PEMFCs) and remains a significant challenge. Covalent organic frameworks (COFs) are an emerging class of porous crystalline materials with tailor-made nanochannels and hold great potential for ion and molecule transport, but their poor chemical stability poses great challenges in this respect. In this contribution, we present a bottom-

The crystal-liquid-glass phase transition of coordination polymers (CPs) and metal-organic frameworks (MOFs) offers attractive opportunities as a new class of amorphous materials. Unlike conventional glasses, coordination chemistry allows the utilization of rational design concepts to fine-tune the desired properties. Although the glassy state has been rare in CPs/MOFs, it exhibits diverse advantages complementary to their crystalline counterparts, including improved mass transport, optical prop

An ionic coordination network consisting of protonated imidazole and anionic one-dimensional chains of Zn(2+) phosphate was synthesized. The compound possesses highly mobile ions in the crystal lattice and behaves as an ionic plastic crystal. The dynamic behavior provides a proton conductivity of 2.6 × 10(-4) S cm(-1) at 130 °C without humidity.

Controlling guests: Porous coordination polymers containing mobile organic groups, such as naphthalene rings (see picture), are synthesized, and their rotational motion is characterized by solid-state 2H NMR spectroscopy. The rotation of the groups can be switched off (blue) by guest (blue spheres) adsorption and switched on (yellow) again by guest desorption. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z603196_s.pdf or from

There are two categories of coordination polymers (CPs): inorganic CPs (i-CPs) and organic ligand bridged CPs (o-CPs). Based on the successful crystal engineering of CPs, we here propose noncrystalline states and functionalities as a new research direction for CPs. Control over the liquid or glassy states in materials is essential to obtain specific properties and functions. Several studies suggest the feasibility of obtaining liquid/glassy states in o-CPs by design principles. The combination o

An interdigitated porous coordination polymer with hydrophobic pore surface shows size and affinity dependent selective gas sorption properties accompanying the reversible structure transformation.

Gas separation properties for CH4/CO2 and CH4/C2H6 of flexible 2D porous coordination polymers under equilibrium gas conditions and mixed gas flow conditions were investigated and the gas separation efficiencies were optimized by precise tuning of the flexibility in ligand-base solid solution compounds.

The glassy state of a two-dimensional (2D) Cd(2+) coordination polymer crystal was prepared by a solvent-free mechanical milling process. The glassy state retains the 2D structure of the crystalline material, albeit with significant distortion, as characterized by synchrotron X-ray analyses and solid-state multinuclear NMR spectroscopy. It transforms to its original crystal structure upon heating. Thus, reversible crystal-to-glass transformation is possible using our new processes. The glass sta

A porous coordination polymer (PCP) with immobilization of sodium cations on the pore surface has been synthesized, by employing a bifunctional carboxylate/sulfonate ligand, and structurally characterized. The porous framework with 1D channels of the dimension of 4.9 x 4.9 A2 shows high thermal stability ( approximately 330 degrees C), affording Type I adsorption isotherms for CO2, acetone, and benzene. The chemical shift of 13C NMR and characteristic adsorption energy (betaE0) of acetone adsorb

The melting behavior of a coordination polymer (CP) crystal was utilized to achieve enhanced and optically switchable proton conductivity in the solid state. The strong acid molecules (triflic acid) were doped in one-dimensional (1D) CP, [Zn(HPO₄ )(H₂ PO₄ )₂ ](ImH₂ )₂ (ImH₂ =monoprotonated imidazole) in the melt state, and overall enhancement in the proton conductivity was obtained. The enhanced proton conductivity is a