There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

다중혈관 관상동맥 환자에서 y-문합을 이용하여 양쪽 내흉동맥만을 사용한 우회술의 조기 성적

Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

The Chemistry and Applications of Metal-Organic Frameworks

J. Appl. Cryst.の発刊に際して

The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.

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Reticular synthesis and the design of new materials

The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.

Functional porous coordination polymers.

슈퍼캐패시터(supercapacitor)는 배터리와 함께 많은 양의 전기에너지를 저장 및 공급하 는 중요한 에너지 저장 장치이다. 특히 슈퍼캐 패시터는 고출력이 가능하고 크기와 형태가 조절가능하여 전자기기 부터 자동차 까지 그 사용분야가 매우 넓다 [1-3]. 최근에 웨어러블 (wearable) 디바이스와 플렉서블(flexible) 전 자기기의 발달과 함께 구부릴 수 있고, 당길 수 있는(stretchable) 슈퍼캐패시터의 개발 또한 활발히 진행되고 있다 [4-8]. 슈퍼캐패시터의 작동원리에 따라 전기이중층 캐패시터(electric double-layer capacitor, EDLC)와 의사캐패시터 (pseudocapacitor)로 나뉜다. EDLC는 전하분 리현상을 이용하기 때문에 넓은 표면적을 갖 는 활성탄(activated carbon)과 같은 전극 재료 를 사용하며 의사캐패시터는 전극 재료의 산 화·환원반응(reduction and oxidation, redox) 을 이용하므로 redox반응을 잘 일으키면서 넓 은 표면적을 갖는 전도성 고분자와 금속산화 물 등의 전극 재료를 사용하게된다 [9]. 슈퍼캐 패시터의 전극 재료로서 높은 에너지 저장능 력 및 성능을 갖으려면, 일반적으로 높은 표면 적을 갖도록 해야하며, 슈퍼캐패시터의 성능 은 전극 활물질의 모폴로지(morphology), 기 공크기분포(pore size distribution), 전기전도 도(electrical conductivity), 표면 특성, 열 특성 등의 다양한 성질에 의해 결정되며, 이를 최적 화 했을 때 높은 성능의 슈퍼캐패시터의 제조 가 가능하다 [1]. 일반적으로 다공성 구조의 카 본 및 금속산화물을 만들기 위해서 그 재료의 전구체를 계면활성제(surfactant)를 이용하여 모폴러지 및 다공성을 조절하였다. 계면활성 제의 사용은 다양한 모양과 구조의 활물질제 조를 가능하게 하였지만, 많은 양의 계면활성 제의 사용은 시약의 가격, 후처리, 환경적인 측 면에서 단점을 가진다. 금속유기구조체(metal-organic frameworks, MOFs)는 금속이온과 유기물 연결체(organic linker)로 만들어진 조성물로서, 합성 시 이러한 추가적인 계면활성제의 사용없이 매우 높은 표 면적을 갖는 금속유기 조성물을 만들 수 있다 (그림 1). 이러한 MOF는 사용되는 금속이온, 유 기연결체, 결정구조 등에 따라 MOF-N, HKUSTN, ZIF-N 등 (N: number)으로 구분되어 명명된 다 (그림 1(b)) [10, 11] . 또한, 사용하는 금속이 온과 유기물 연결체의 종류에 따라 다공성 특 성을 조절할 수 있고, 이들의 열처리를 통해서 다공성 카본체 및 금속산화물의 제조가 가능하 다 [12]. 더욱이, MOF는 기존의 다양한 재료에 적용이 가능하여 다양한 에너지저장 재료로 만 들어 질 수 있으며, 나노기술 및 다양한 접근 방 법을 통해 나노구조체 및 조성물의 합성이 가 능하다 [13]. 이러한 장점으로 인해 최근 많은 종류의 MOF 물질들이 슈퍼캐패시터 및 2차전 지의 에너지 저장시스템(energy storage systems, ESSs) 에 응용되고 있다 (그림 2). MOF 중 이미다졸(imidazole) 유도체를 유기연결체로

Metal–Organic Frameworks (MOFs)

Encapsulating guest molecules inside host structures ranging from soft, flexible enzymes to rigid, porous zeolites has led to developments in many areas, including catalysis, sensing and separation. This Review highlights how metal–organic frameworks — materials formed by linking metal centres with organic ligands — can combine softness with regularity to produce dynamic, yet crystalline, structures that may prove useful for a range of applications.
 The field of host–guest complexation is intensely attractive from diverse perspectives, including materials science, chemistry and biology. The uptake and encapsulation of guest species by host frameworks are being investigated for a wide variety of purposes, including separation and storage using zeolites, and recognition and sensing by enzymes in solution. Here we focus on the concept of the cooperative integration of 'softness' and 'regularity'. Recent developments on porous coordination polymers (or metal–organic frameworks) have provided the inherent properties that combine these features. Such soft porous crystals exhibit dynamic frameworks that are able to respond to external stimuli such as light, electric fields or the presence of particular species, but they are also crystalline and can change their channels reversibly while retaining high regularity. We discuss the relationship between the structures and properties of these materials in view of their practical applications.

Soft porous crystals

Metal-organic microporous materials (MOMs) have attracted wide scientific attention owing to their unusual structure and properties, as well as commercial interest due to their potential applications in storage, separation and heterogeneous catalysis. One of the advantages of MOMs compared to other microporous materials, such as activated carbons, is their ability to exhibit a variety of pore surface properties such as hydrophilicity and chirality, as a result of the controlled incorporation of organic functional groups into the pore walls. This capability means that the pore surfaces of MOMs could be designed to adsorb specific molecules; but few design strategies for the adsorption of small molecules have been established so far. Here we report high levels of selective sorption of acetylene molecules as compared to a very similar molecule, carbon dioxide, onto the functionalized surface of a MOM. The acetylene molecules are held at a periodic distance from one another by hydrogen bonding between two non-coordinated oxygen atoms in the nanoscale pore wall of the MOM and the two hydrogen atoms of the acetylene molecule. This permits the stable storage of acetylene at a density 200 times the safe compression limit of free acetylene at room temperature.

Highly controlled acetylene accommodation in a metal–organic microporous material

In a decade, many porous coordination polymers have been synthesized, providing a variety of properties ranging from storage, separation, exchange of guests in their cavities, magnetism, conductivity and catalysis by their frameworks. In this tutorial review, we focus on the hydrogen bonding type arrangements for dynamic porous coordination polymers exhibiting elastic guest accommodations, in contrast to rigid three-dimensional (3-D) frameworks. Such dynamic porous properties induce highly-selective guest accommodation and magnetic modulation, and could now be considered a new class of practical materials.

Susumu Kitagawa

Papers

Functional porous coordination polymers.

Metal–Organic Frameworks (MOFs)

Soft porous crystals

Highly controlled acetylene accommodation in a metal–organic microporous material

Dynamic porous properties of coordination polymers inspired by hydrogen bonds