Takashi Uemura

Metal-organic frameworks (MOFs) have received much attention because of their attractive properties. They show great potential applications in many fields. An emerging trend in MOF research is hybridization with flexible materials, which is the subject of this review. Polymers possess a variety of unique attributes, such as softness, thermal and chemical stability, and optoelectrical properties that can be integrated with MOFs to make hybrids with sophisticated architectures. Hybridization of MO

Prussian blue (PB) nanoparticles protected by poly(vinylpyrrolidone) (PVP) were prepared by mixing aqueous Fe2+, Fe(CN)63-, and PVP solutions together and were characterized by UV-vis, IR, XRPD, and TEM. Averaged dimensions of the nanoparticles were controlled between 12 and 27 nm depending on initial Fe ion concentrations and feed ratios of Fe ion to PVP. Solubility of PB bulk in organic solvents is considerably low; nevertheless, formations of the PB nanoparticles dramatically increase the sol

Porous coordination polymers (PCPs) have been recently highlighted because of their high synthetic designability in structure and functions. Because of their ordered nanoporous structures with a large surface area and tunable pore surface functionality, PCPs have emerged as a significant class of nanoporous materials with potential applications in gas storage, separation, catalysis, and chemical sensing. Recent research has shown the utility of PCPs as host materials for the confinement of nanop

The thermal transitions of confined polymers are important for the application of polymers in molecular scale devices and advanced nanotechnology. However, thermal transitions of ultrathin polymer assemblies confined in subnanometre spaces are poorly understood. In this study, we show that incorporation of polyethylene glycol (PEG) into nanochannels of porous coordination polymers (PCPs) enabled observation of thermal transitions of the chain assemblies by differential scanning calorimetry. The

Get into the groove: Porous coordination polymers with basic interaction sites catalyze the fast and stereoselective polymerization of acetylene derivatives. The reactions take place in the one-dimensional nanochannels of the coordination polymer (see picture). Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z600333_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any su

Radical polymerization of vinyl monomers (styrene, methyl methacrylate, and vinyl acetate) was performed in various nanochannels of porous coordination polymers (PCPs), where relationships between the channel size and polymerization behaviors, such as monomer reactivity, molecular weight, and stereostructure, were studied. The capability for precise size tuning of nanospaces has afforded the first systematic study of radical polymerization in microporous channels based on PCPs. In this polymeriz

Prussian blue (PB) nanoparticles protected by organic polymers such as poly(vinylpyrrolidone) (PVP) and poly(diallyldimethylammonium chloride) (PDDA) were prepared. Different experimental conditions (concentrations of Fe ions and feed ratios of Fe to the polymers) have been investigated to control the size of the PB nanoparticles. For example, the averaged dimensions of the PB nanoparticles were tuned from 12 to 27 nm by use of PVP in the different conditions. Addition of PDDA produced the PB na

The first radical polymerisation of styrene in porous coordination polymers has been carried out, providing stable propagating radicals (living radicals), and a specific space effect of the host frameworks on the monomer reactivity is demonstrated.

Molecules confined in nanospaces will have distinctly different properties to those in the bulk state because of the formation of specific molecular assemblies and conformations. We studied the chain conformation and dynamics of single polystyrene (PSt) chains confined in highly regular one-dimensional nanochannels of a porous coordination polymer [Zn 2(bdc) 2ted] n ( 1; bdc = 1,4-benzenedicarboxylate, ted = triethylenediamine). Characterization by two-dimensional (2D) heteronuclear (1)H- (13)C

In the groove: Radical polymerization of divinylbenzenes (DVBs) in the one-dimensional nanochannels of porous coordination polymers allows linearly extended topotactic polymerization without cross-linking (see picture). The main factors that influence this polymerization are the channel size and host framework flexibility. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z700242_s.pdf or from the author. Please note: The publishe

Inspired by elegant polymerizations in biological systems, polymer synthesis in confined artificial nanospaces is a key challenge in the control of polymer structures and the design of well-defined nanostructures. In this regard, porous coordination polymers (PCPs) have a wide range of advantages, such as regular channel structures, controllable pore size, dynamic and flexible pores, and unique surface potentials and functionality, which can be utilized for precisely controlled polymerization an

Systematic functionalization of porous coordination polymers (PCPs), [Cu(2)(L)(2)(ted)](n) (where L = dicarboxylates and ted = triethylenediamine), by introducing various substituents onto the component organic ligand, L, was performed to regulate the radical polymerization of methyl methacrylate (MMA) in the nanochannels. The effect of the substituent groups on stereoregularity of the resulting poly(methyl methacrylate) (PMMA) was observed, where the tacticity of the PMMA strongly depended on t

Oxidative polymerization of pyrrole in the 3D nanochannels of [Cu3(BTC)2]n (BTC = benzene-1,3,5-tricarboxylate) produced polypyrrole (PPy) inside the framework. Subsequent isolation of PPy by dissolution of the host framework in ammonia solution gave a functional porous PPy, which contrasts with the conventional bulk-synthesized PPy system.

We report on the formation of single poly(N-vinylcarbazole) (PVCz) chains in one-dimensional channels of [La(1,3,5-benzenetrisbenzoate)](n), where the side carbazolyl groups of the confined PVCz are effectively π-stacked. This ideal conformation of PVCz chains in the coordination nanochannels contributed to a drastic increase in hole mobility, which was 5 orders of magnitude higher than that in the bulk state. It is also noteworthy that PVCz isolated from the nanchannels still had a high hole mo

This short review focuses on recent developments in polymerization reactions using metal-organic frameworks (MOFs). MOFs are crystalline porous materials that are able to tune their frameworks, enabling their use as promising media for polymerization. The precise design of the MOF structure is key to controlling polymerizations, allowing for the regulation of not only primary but also higher-order structures.