{"title":"Photofunctional Organosilicon Compounds","authors":"Masaki Nakae, Masaki Nishio, Y. Yamanoi","doi":"10.4019/bjscc.76.31","DOIUrl":"https://doi.org/10.4019/bjscc.76.31","url":null,"abstract":"","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":"76 1","pages":"31-39"},"PeriodicalIF":0.0,"publicationDate":"2020-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47308043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Proton-responsive pincer-type ligands have been used as scaffolds to realize metal–ligand cooperative transformations. Unlike most of the ligands therein, 2,6-bis(pyrazol-3-yl)pyridines (3-bpp) ensure that two protic groups point to the remaining coordination site in the pincer plane. This article reviews the coordination chemistry of 3-bpp and related tridentate ligands with emphasis on the characteristics originating from the Brønsted acidity of the peripheral NH groups. Synthesis of 3-bpp complexes, which often associated with spontaneous deprotonation of the 3-bpp ligand and aggregation of the complex to give supramolecular structures, is first described. Deprotonation of the 3-bpp complexes along with the following reactivities is then discussed. Application of the 3-bpp complexes to catalytic reactions as well as materials exhibiting spin-crossover and fluorescence is also described. Finally, pincer-type complexes bearing protic N -heterocyclic carbene side arms are briefly mentioned as relevant molecules.
{"title":"Coordination Chemistry of Protic Pincer-Type Bis(pyrazolyl)pyridines and Related Compounds","authors":"S. Kuwata","doi":"10.4019/bjscc.76.21","DOIUrl":"https://doi.org/10.4019/bjscc.76.21","url":null,"abstract":"Proton-responsive pincer-type ligands have been used as scaffolds to realize metal–ligand cooperative transformations. Unlike most of the ligands therein, 2,6-bis(pyrazol-3-yl)pyridines (3-bpp) ensure that two protic groups point to the remaining coordination site in the pincer plane. This article reviews the coordination chemistry of 3-bpp and related tridentate ligands with emphasis on the characteristics originating from the Brønsted acidity of the peripheral NH groups. Synthesis of 3-bpp complexes, which often associated with spontaneous deprotonation of the 3-bpp ligand and aggregation of the complex to give supramolecular structures, is first described. Deprotonation of the 3-bpp complexes along with the following reactivities is then discussed. Application of the 3-bpp complexes to catalytic reactions as well as materials exhibiting spin-crossover and fluorescence is also described. Finally, pincer-type complexes bearing protic N -heterocyclic carbene side arms are briefly mentioned as relevant molecules.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41913518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Porous materials, including porous carbons, zeolites, and porous coordination polymers (PCPs), are generally recognized as rigid, hard, and fragile substances. However, focusing on their structure and surface at the molecular level, there are various dynamic phenomena and processes such as deformation and reconstruction of the crystal structure as well as molecular motion such as vibration and rotation occurring in the materials. In this account, recent developments of functional PCPs based on a new design approach making use of such dynamic nature of molecular entities are described. A dynamic molecular functionality incorporated into the PCP nanochannel affords precise control of gas diffusion process in the PCP, thus enabling outstanding gas separation and storage capability. In order to visualize the dynamic behavior of PCP, atomic force microscopy was used to observe native surfaces of a PCP crystal, which enabled real-time imaging of the dynamic response of the PCP with a molecular-level resolution. In addition, an interdisciplinary approach that combines porous material chemistry and soft material chemistry, which gives novel porous soft materials with solution/thermal processable feature, is described. This bottom-up design concept that connects dynamic molecular properties to the material functions offers a promising way to the next-generation porous materials.
{"title":"Design and Application of Porous Coordination Materials with Soft and Dynamic Nature","authors":"Nobuhiko Hosono","doi":"10.4019/bjscc.75.42","DOIUrl":"https://doi.org/10.4019/bjscc.75.42","url":null,"abstract":"Porous materials, including porous carbons, zeolites, and porous coordination polymers (PCPs), are generally recognized as rigid, hard, and fragile substances. However, focusing on their structure and surface at the molecular level, there are various dynamic phenomena and processes such as deformation and reconstruction of the crystal structure as well as molecular motion such as vibration and rotation occurring in the materials. In this account, recent developments of functional PCPs based on a new design approach making use of such dynamic nature of molecular entities are described. A dynamic molecular functionality incorporated into the PCP nanochannel affords precise control of gas diffusion process in the PCP, thus enabling outstanding gas separation and storage capability. In order to visualize the dynamic behavior of PCP, atomic force microscopy was used to observe native surfaces of a PCP crystal, which enabled real-time imaging of the dynamic response of the PCP with a molecular-level resolution. In addition, an interdisciplinary approach that combines porous material chemistry and soft material chemistry, which gives novel porous soft materials with solution/thermal processable feature, is described. This bottom-up design concept that connects dynamic molecular properties to the material functions offers a promising way to the next-generation porous materials.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42594123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Functional Studies on Hemoproteins and Heme-enzymes Based on Their Molecular Structures","authors":"Y. Shiro","doi":"10.4019/bjscc.75.51","DOIUrl":"https://doi.org/10.4019/bjscc.75.51","url":null,"abstract":"","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49640398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
環境の変化や外部刺激に応答して働き(機能・物性)が 変わる物質は,応答性機能材料として注目を集めている 。 一般的に,材料などの働きを変えるためには,その物質の 分子構造を変化させる必要がある。したがって,応答性機 能材料を開発するためには,環境の変化や外部刺激に応答 して構造が変化する分子を用意する必要がある。 これらの応答性分子には,外部刺激などに対して直接 的に応答する部分構造が必須となる。光や電気刺激 を 使うシステムがよく知られているが,アミノ基やカルボキ シ基などのありふれた官能基でも,プロトン(pH変化) に応答する部分構造として働き得る 。さらには,無機イ オンや有機分子の認識によって働きが変わる人工,生体 分子などもこのカテゴリーに属する 。このような刺激応 答に連動させることで,これまでに様々な分子構造の動的 変換が達成されてきた。特に,弱い結合,すなわち非共 有結合によって作られる超分子構造や集合構造の中には, 構成要素中の微小な分子構造の変化が敏感に反映されて 巨大な構造の形状変化を実現できる例 もあり,応答性機 能材料の創製の一つの重要な手法となっている。 金属錯体に含まれる配位結合は,溶液中で結合の組み 換え(配位子置換)を起こしやすいという動的特性を有 する (Fig. 1a)。このことを考えると,金属錯体は,動的 構造変換を起こすための基本骨格として有用であると思 われる。配位子置換反応の起こりやすさは,金属の種類 や酸化数,配位子との組み合わせによって変わる。置換 活性錯体(1分以内に配位子置換を起こす錯体 )だけ でなく,置換不活性錯体の中にも数時間スケールでみれ ば配位子置換を起こすものも多く知られており,これら を含めれば,かなり多くの錯体は動的な特性を有してい るといえる。つまり,一般的な有機物のように共有結合 のみで構築された分子と比べて,金属錯体は,より動的 なプラットフォームを提供できる。それでいて配位結合 は,クーロン力,疎水効果,水素結合など他の非共有結 合と比べて結合距離や方向性などが明確に定まってい る。この点が,分子構造をもとに精密に設計した構造・ 機能の変換を実現するためのプラットフォームとして, 金属錯体骨格が最適である理由となる。 Metal complexes are generally dynamic due to the reversibility of formation/cleavage of the coordination bonds. Therefore, metal complexes could be used as platforms for switchable functional molecules with dynamic structural changes. In order to achieve structural conversions as intended, finely designed organic frameworks as well as metal centers with appropriate lability are necessary. For this purpose, the author has focused on macrocyclic, acyclic, and cage-like oligosalen structures, which can incorporate multiple metal centers at desired positions. In this review, various kinds of dynamic structural conversions, such as helicity inversion of helical complexes and open/close functions of molecular cage structures, which were developed by the author and coworkers, are described.
响应环境的变化和外部刺激而作用（功能·物性）发生变化的物质，作为响应性功能材料受到关注。一般来说，为了改变材料等的作用，需要改变该物质的分子结构。因此，为了开发响应性功能材料，需要准备响应环境变化和外部刺激而结构变化的分子。这些响应性分子需要对外部刺激等直接响应的部分结构。使用光和电刺激的系统众所周知，即使是氨基和羧基等常见的官能团，也可以作为响应质子（pH变化）的部分结构发挥作用。而且，根据无机离子和有机分子的认识，作用发生变化的人工、生物分子等也属于这一范畴。通过与这样的刺激响应联动，到目前为止已经实现了各种分子结构的动态转换。特别是在通过弱键，即非共价键形成的超分子结构和集合结构中，也有敏感地反映构成要素中微小分子结构的变化而能够实现巨大结构的形状变化的例子，成为创造响应性功能材料的一种重要方法。金属络合物中含有的配位键具有在溶液中容易引起键的重组（配体置换）的动态特性（Fig.1a）。考虑到这一点，我们认为金属络合物作为引起动态结构转换的基本骨架是有用的。配体置换反应的容易发生程度根据金属的种类和氧化数、与配体的组合而变化。不仅是取代活性络合物（1分钟以内发生配体取代的络合物），在取代惰性络合物中，从数小时尺度来看也有很多发生配体取代的络合物，如果包含这些，可以说相当多的络合物具有动态特性。也就是说，与一般的有机物那样只通过共价键构建的分子相比，金属络合物可以提供更动态的平台。而且配位结合与库仑力、疏水效果、氢键等其他非共价结合相比，结合距离和方向性等明确确定。这一点是金属络合物骨架作为实现以分子结构为基础精密设计的结构、功能转换的平台最合适的理由。Metal complexes are generally dynamic due to the reversibility of formation/cleavage of the coordination bonds。Therefore，metal complexes could be used as platforms for switchable functional molecules with dynamic structural changes。Inorder to achieve structural conversions as intended，finely designed organic frameworks as well as metal centers with appropriate lability are necessary。Forthis purpose，the author has focused on macrocyclic，acyclic，and cage-like oligosalen structures，which can incorporate multiple metal centers at desired positions。In this review，various kinds of dynamic structural conversions，such as helicity inversion of helical complexes and open/close functions of molecular cage structures，which were developed by the author and coworkers，are described。
{"title":"Design and Synthesis of Responsive Functional Molecules Based on Metal Complexes and Their Dynamic Structural Conversions","authors":"Shigehisa Akine","doi":"10.4019/bjscc.75.13","DOIUrl":"https://doi.org/10.4019/bjscc.75.13","url":null,"abstract":"環境の変化や外部刺激に応答して働き(機能・物性)が 変わる物質は,応答性機能材料として注目を集めている 。 一般的に,材料などの働きを変えるためには,その物質の 分子構造を変化させる必要がある。したがって,応答性機 能材料を開発するためには,環境の変化や外部刺激に応答 して構造が変化する分子を用意する必要がある。 これらの応答性分子には,外部刺激などに対して直接 的に応答する部分構造が必須となる。光や電気刺激 を 使うシステムがよく知られているが,アミノ基やカルボキ シ基などのありふれた官能基でも,プロトン(pH変化) に応答する部分構造として働き得る 。さらには,無機イ オンや有機分子の認識によって働きが変わる人工,生体 分子などもこのカテゴリーに属する 。このような刺激応 答に連動させることで,これまでに様々な分子構造の動的 変換が達成されてきた。特に,弱い結合,すなわち非共 有結合によって作られる超分子構造や集合構造の中には, 構成要素中の微小な分子構造の変化が敏感に反映されて 巨大な構造の形状変化を実現できる例 もあり,応答性機 能材料の創製の一つの重要な手法となっている。 金属錯体に含まれる配位結合は,溶液中で結合の組み 換え(配位子置換)を起こしやすいという動的特性を有 する (Fig. 1a)。このことを考えると,金属錯体は,動的 構造変換を起こすための基本骨格として有用であると思 われる。配位子置換反応の起こりやすさは,金属の種類 や酸化数,配位子との組み合わせによって変わる。置換 活性錯体(1分以内に配位子置換を起こす錯体 )だけ でなく,置換不活性錯体の中にも数時間スケールでみれ ば配位子置換を起こすものも多く知られており,これら を含めれば,かなり多くの錯体は動的な特性を有してい るといえる。つまり,一般的な有機物のように共有結合 のみで構築された分子と比べて,金属錯体は,より動的 なプラットフォームを提供できる。それでいて配位結合 は,クーロン力,疎水効果,水素結合など他の非共有結 合と比べて結合距離や方向性などが明確に定まってい る。この点が,分子構造をもとに精密に設計した構造・ 機能の変換を実現するためのプラットフォームとして, 金属錯体骨格が最適である理由となる。 Metal complexes are generally dynamic due to the reversibility of formation/cleavage of the coordination bonds. Therefore, metal complexes could be used as platforms for switchable functional molecules with dynamic structural changes. In order to achieve structural conversions as intended, finely designed organic frameworks as well as metal centers with appropriate lability are necessary. For this purpose, the author has focused on macrocyclic, acyclic, and cage-like oligosalen structures, which can incorporate multiple metal centers at desired positions. In this review, various kinds of dynamic structural conversions, such as helicity inversion of helical complexes and open/close functions of molecular cage structures, which were developed by the author and coworkers, are described.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49490771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
using density functional theory calculations. An important feature in the reaction is the spin crossover between the high-spin and low-spin potential energy surfaces in particular in the C–H activation process, the energy barrier of which is significantly decreased by the spin inversion. These mechanistic insights are reasonably extended to Fe, Co, Ni, and Cu-exchanged zeolites and IrO 2 and β-PtO 2 (110) surfaces.
{"title":"Studies of Orbital Principle for Methane Activation Using Computational Quantum Chemistry","authors":"Yoshizawa Kazunari","doi":"10.4019/bjscc.75.57","DOIUrl":"https://doi.org/10.4019/bjscc.75.57","url":null,"abstract":"using density functional theory calculations. An important feature in the reaction is the spin crossover between the high-spin and low-spin potential energy surfaces in particular in the C–H activation process, the energy barrier of which is significantly decreased by the spin inversion. These mechanistic insights are reasonably extended to Fe, Co, Ni, and Cu-exchanged zeolites and IrO 2 and β-PtO 2 (110) surfaces.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46415951","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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