Bulletin of Japan Society of Coordination Chemistry最新文献_第10页

The Diversity of the Metal-Ligand Interplay in Coordination Chemistry† 配位化学中金属-配体相互作用的多样性

Bulletin of Japan Society of Coordination Chemistry Pub Date : 2014-05-31 DOI: 10.4019/BJSCC.63.19

P. Braunstein

{"title":"The Diversity of the Metal-Ligand Interplay in Coordination Chemistry†","authors":"P. Braunstein","doi":"10.4019/BJSCC.63.19","DOIUrl":"https://doi.org/10.4019/BJSCC.63.19","url":null,"abstract":"On the occasion of the 63th Conference of the Japan Society of Coordination Chemistry, held in Okinawa from November 2-4, 2013, it appears appropriate to recall that this year marks the 100th anniversary of the award of the Nobel Prize to Alfred Werner (1866-1919) \"in recognition of his work on the linkage of atoms in molecules by which he has thrown new light on earlier investigations and opened up new fields of research especially in inorganic chemistry\". His pioneering achievements laid the foundation of Coordination Chemistry. Elucidating the nature of the metal-ligand interactions and recognizing their central role in determining the structures and properties of coordination complexes soon became subjects of major endeavour. The complexity of some of the ligands used today contrasts with those found in Wernerʼs chemistry (halides, water, ammonia, ethylenediamine,...) and they often require multistep organic synthesis. Interestingly, in the days of this chemistry giant, the notion that metal-metal bonding could occur within molecules, and not only within bulk metals, was non-existent. Later on, it was recognized that such bonding could exist and be responsible for holding together dior trinuclear complexes, as in [Mn2(CO)10] 2 or [Ru3(CO)12]. 3 The new and fast growing field of cluster chemistry became coined a “post-Wernerian chemistry”. Already in 1999, a 3 volumes book was not sufficient to cover all the aspects of the synthetic, structural and theoretical chemistry of metal clusters and their diverse applications in numerous fields of modern science. In this Account, we shall examine selected examples of complexes in which the ligands play an essential role in determining the overall molecular properties. We will limit ourselves to those relevant to catalytic applications in ethylene oligomerization. Some polynuclear complexes and metal clusters, where the nuclearity and the nature of the metals present are of primary concern, will also be discussed. The molecular chemistʼs toolbox allows the combination of ligands, which can range from a single atom to complex biorelevant molecules, and metals to form monoor polynuclear metal complexes. When metal centres are associated within the same molecule through metal-metal interactions, clusters This Account will focus on some recent aspects of the research performed in the authorʼs laboratory. Selected examples of complexes in which the ligands play an essential role in determining the molecular properties will be examined. Concerning the applications of these complexes, we will limit ourselves to some aspects related to the catalytic oligomerization of ethylene. In the search for such catalysts, we found that deprotonation of N,OH ligands chelated to Ni(II) with NaH can give rise to a range of heterometallic Na-Ni polynuclear complexes. In addition to their catalytic relevance, their magnetic properties were also investigated and have revealed in some cases Single Molecule Magnet behaviour. The","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2014-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.63.19","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70512805","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}

引用次数: 0

Photophysical Properties of Transition Metal Complexes under Rigid Environments 刚性环境下过渡金属配合物的光物理性质

Bulletin of Japan Society of Coordination Chemistry Pub Date : 2014-05-31 DOI: 10.4019/BJSCC.63.46

A. Ito

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Surface Modification of Coordination Polymers with Biomolecules for Cellular Uptake 生物分子配位聚合物的表面修饰及细胞摄取

Bulletin of Japan Society of Coordination Chemistry Pub Date : 2014-01-01 DOI: 10.4019/BJSCC.64.25

T. Koshiyama

{"title":"Surface Modification of Coordination Polymers with Biomolecules for Cellular Uptake","authors":"T. Koshiyama","doi":"10.4019/BJSCC.64.25","DOIUrl":"https://doi.org/10.4019/BJSCC.64.25","url":null,"abstract":"Coordination polymers (CPs) or metal-organic frameworks (MOFs) are attractive porous materials because of their potential applications such as molecular storage, separation, heterogeneous catalysis, chemical sensing and others. Recently, nano-sized MOFs have been studied as drug delivery vehicles and biomedical imaging agents. Despite the growing interest on MOFs in the biological field, their instability and poor biocompatibility restrict their application to biomaterials. In order to improve the stability and to provide biocompatibility, surface modification of MOFs has been advanced by using a thin silica shell, hydrophilic organic polymers (PEG and PVP) and biomolecules. In this topic, I focus on the recent researches on the surface modification of MOF nanoparticles with biomolecules such as nucleic acid, lipid bilayer and protein. The MOF nanoparticles covered with biomolecules exhibit increased stability under physiological condition, and enhanced cellular uptake compared with unmodified MOF nanoparticles. These results clearly indicate that biomolecule conjugation to MOFs is a useful strategy for creating novel biomaterials. Fig. 1 (a) Structure of [Zr6(m3-O)4(m3-OH)4(C8H3O4)6] (UiO66)4), (b) Surface modification of UiO-66-N3 nanoparticles dibenzylcyclooctyne (DBCO) functionalized DNA.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2014-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.64.25","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70513375","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}

引用次数: 0

Recent Trend in the Measurements of Luminescence Spectra and Quantum Yields of Metal Complexes 金属配合物发光光谱和量子产率测量的最新进展

Bulletin of Japan Society of Coordination Chemistry Pub Date : 2014-01-01 DOI: 10.4019/BJSCC.64.14

Hitoshi Ishida

{"title":"Recent Trend in the Measurements of Luminescence Spectra and Quantum Yields of Metal Complexes","authors":"Hitoshi Ishida","doi":"10.4019/BJSCC.64.14","DOIUrl":"https://doi.org/10.4019/BJSCC.64.14","url":null,"abstract":"近年、有機 EL材料やセンサー分子など発光材料開発研究の発展により発光性金属錯体への注目が集まったことから 1, 、多くの研究者が発光性金属錯体の開発や光物性研究に取り組むようになった。その結果、金属錯体の発光物性に関する研究が、錯体化学討論会をはじめ関連するジャーナルから発表される件数が急激に増加しているが、中には発光現象に関する知識が不十分なままデータを発表するケースも多く見られている。背景には、発光測定に不慣れな合成化学者が、「装置にサンプルをセットしてボタンを押す(あるいはクリックする)だけで信頼できる結果(スペクトル等)が得られる」と信じていることがあるようだ。実際、サンプル調製上の問題のために正しい結果が得られないだけでなく、装置の校正が不十分なために正しい結果が得られていない場合も多く見られる。新規な化合物を合成した研究者が結果を報告する場合、比較できるデータがないために間違いに気付きにくい。測定条件やサンプル調製、また測定装置の原理の概略を理解するだけで、間違いのかなりの部分は防げるように思われるが、金属錯体分野から光化学分野に参入した研究者にとって、どのように勉強すればよいのかはわかりにくいようだ。金属錯体の光化学分野では、配位化合物の光物理・光化学に関する国際会議 (International Symposium on the Photophysics and Photochemistry of Coordination Compounds)が 2年に一度開催されている。この分野における急激な研究者人口の増大と、検討不十分な研究発表の増加が憂慮されため、2009年に札幌で行われた第 18回シンポジウムにおいて、発光測定に関する問題点を議論する特別セッションが設けられた。この機会に、IUPAC Inorganic Chemistry Divisionに無機化合物の発光スペクトルおよび量子収率測定のガイドラインを作成するプロジェクト “Guidelines for Measurement of Luminescence Spectra and Quantum Yields of Inorganic Compounds, Metal Complexes and Materials (Project No.: 2009-045-1-200)” を立ち上げることが話し合われ、石田が Chairとして提案させていただいた。プロジェクトメンバーは、Beeby, Andrew (Durham University, UK), Bünzli, Jean-Claude G.(EPFL, Switzerland), Campagna, Sebastiano (University of Messina, Italy), De Cola, Luisa (University of Strasbourg, France), Ford, Peter (University of California Santa Barbara, USA), Gordon, Keith (Otago University, New Zealand), Hasegawa, Yasuchika (Hokkaido University, Japan), Hasegawa, Miki (Aoyama Gakuin University, Japan), Katoh, In a luminescent metal complex, the singlet excited state readily converts the excitation energy to the triplet state by increasing the spin-orbit coupling due to the presence of a heavy atom such a metal ion. The emission is called phosphorescence, which can be frequently observed even at room temperature. This review indicates the problems that inorganic chemists may confront while measuring the emission spectra and the emission quantum yields of metal complexes and introduces the IUPAC project to prepare the guidelines for the measurements. Common textbooks in photochemistry usually aim at the physical and/or organic chemists, and they are not always suitable for inorganic chemists who measure the room-temperature phosphorescence. This review describes the procedures for measuring the emission spectra and the quantum yields of the metal complexes in solution from the viewpoints of selection of solvent, sample concentration, de-aeration, and temperature control. It describes both the relative and absolute methods to determine the emission quantum yields. It further indicates that the measurements of solid-state samples are much more difficult than solutions and recommends that the experimental conditions are reported in as much details as possible.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2014-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.64.14","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70513244","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}

引用次数: 1

Developments in Silica-Based Nanoporous Materials 硅基纳米多孔材料的研究进展

Bulletin of Japan Society of Coordination Chemistry Pub Date : 2014-01-01 DOI: 10.4019/BJSCC.64.2

K. Kuroda

{"title":"Developments in Silica-Based Nanoporous Materials","authors":"K. Kuroda","doi":"10.4019/BJSCC.64.2","DOIUrl":"https://doi.org/10.4019/BJSCC.64.2","url":null,"abstract":"無機化学の中で錯体化学とケイ酸塩化学はともに独自の歴史を有しているが、両分野に跨る研究も古くから知られている。[SiO4]四面体が二次元的に連結して層状ケイ酸塩が形成されるが、中でも層状粘土鉱物層間に金属錯体をインターカレートさせて、錯体の構造変化や物性上の特徴を調査するなどの研究は、古くから知られている。層状粘土鉱物中のケイ酸塩シート上の空隙配列を活かした錯体の光学分割、三次元ケイ酸塩骨格を有する結晶性ミクロ多孔質のゼオライト内への錯体導入や機能発現など多くの報告がある。最近の PCP/MOFの発展により多孔質体の化学が大きな変貌をとげている。多孔質体化学としてはミクロ多孔質結晶として古くから知られているゼオライトや 1980 年代終盤から始まったメソ多孔体があり、それらはシリカ・ケイ酸塩化学が基盤となり、大きく展開されてきた。これらの物質群が今後も大きく発展することが期待されている状況下、本 Accountsでは筆者らのシリカ・ケイ酸塩系多孔質物質研究に関わる研究成果を中心に紹介し、今後の展開に資することを目的としている。","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2014-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.64.2","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70513311","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}

引用次数: 0

Luminescent Mechanochromism and Spontaneous Phase Transformation of Gold(I) Isocyanide Complexes 金(I)异氰化物配合物的发光机械变色和自发相变

Bulletin of Japan Society of Coordination Chemistry Pub Date : 2013-11-30 DOI: 10.4019/BJSCC.62.3

Hajime Ito, T. Seki

引用次数: 1

Homogeneous Catalysis of Nickel(II) Complexes Promoting Hydrogen Production with High Turnover Numbers 镍(II)配合物促进高周转率制氢的均相催化作用

Bulletin of Japan Society of Coordination Chemistry Pub Date : 2013-11-30 DOI: 10.4019/BJSCC.62.26

K. Yamauchi

引用次数: 1

Harmony of π-π Stacking Interaction and Metal Complexation to Generate Molecular Functional Emergence π-π叠层相互作用与金属络合的和谐产生分子功能涌现

Bulletin of Japan Society of Coordination Chemistry Pub Date : 2013-11-30 DOI: 10.4019/BJSCC.62.12

Y. Yamada, Kentaro Tanaka

{"title":"Harmony of π-π Stacking Interaction and Metal Complexation to Generate Molecular Functional Emergence","authors":"Y. Yamada, Kentaro Tanaka","doi":"10.4019/BJSCC.62.12","DOIUrl":"https://doi.org/10.4019/BJSCC.62.12","url":null,"abstract":"分子組織化学は、組織化された分子間の相互作用によって、個々の分子からは得られない、新しい反応性、電子特性、磁性など創発的な機能を引き出すことを目的としている。このような分子組織を創製するためには、自在な次元的空間設計、精密な分子合成、および多数・多種の分子コンポーネントの自己組織化を通し、階層的にプログラムされた物質構築が重要な鍵となる。分子組織の構築において、生体分子組織の階層性は示唆に富んでいる。基本的なビルディングブロック分子 (アミノ酸、ヌクレオシド、糖、脂質など )が配列化し、「数」、「組成」、「配列」、「方向」に分布を持たないファインな分子として、タンパク質、DNA、RNA、多糖などの生体高分子の一次構造が形づくられ、それらが厳密な「選択性」の上で、正確な「空間配置」をとりながら組織化し、適切な「タイミング」で高度な機能を発現している。これらの機能は、個々のビルディングブロック分子からは予想もできない創発的なものであり、分子組織構築の様々なヒントが散見できる。多数・多種類のコンポーネントから分子組織を構築するために、また外部刺激に応答する柔軟性を有する分子組織を構築するために、非共有結合性の弱い相互作用、すなわち水素結合や ppスタッキング相互作用、金属配位結合などを利用することは、極めて有効である。本稿では特に、芳香族性の分子の ppスタッキング相互作用によって構築される「場」と金属錯体とのハーモニーによって生み出される機能性分子組織の構築について概観したい。本論に入る前に、芳香族性分子の p-pスタッキング相互作用について整理しておく。芳香族性分子は、(1) 平面性もしくは直線性が高い、(2) 非芳香族性分子に比べて小さな HOMO-LUMOギャップをもつ、(3) 非芳香族性分子に比べて分極しやすい、などの特性を示す。3次元の p-pスタッキング構造をデザインするための重要なキーポイントが、特に (1)および (3)に見られる。大きな分極率を示す芳香族性分子では、分子内に誘起双極子が生じやすいため、誘起双極子間の相互作用 (分散力 ) が、芳香族性分子間の p-p相互作用に大きく寄与している。さらに、平面性の分子同士が面と面を向かい合わせて接することにより、分散力の効果が最大限に活かされることとなり、いわゆる face-to-faceの会合様式が形成される。同種の芳香族性分子間の会合では、分子内の電荷分布によって、分子同士が平行に少しずれた形でスタッキングした構造 (Fig. 1b)や、サイドオン (ヘリンボーン )型の構造 (Fig. 1c)が多くみられる。一方、異なる 2種類の In this review, we focus on the integrated assemblies of metal complexes and their functional emergence generated by the synergy effects of p-p stacking interaction and metal complexation. Programmable construction of integrated molecular assemblies is the best measure for bringing out the emergent functions which can be evolved from the intermolecular communications of functional molecular components. Combination of p-p stacking interaction and metal complexation allows not only to reinforce the mutual interactions but also to generate the emergent intermolecular communications. This review introduces the recent studies including the synergy effects on electrical, magnetic, catalytic and molecular recognition functions in soft, crystalline and single molecular materials.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2013-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.62.12","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70512829","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}

引用次数: 1

Recent Researches on Hydrogen Generation Reaction Catalyzed by Group 8 Transition-Metal Complex 8族过渡金属配合物催化制氢反应的研究进展

Bulletin of Japan Society of Coordination Chemistry Pub Date : 2013-11-30 DOI: 10.4019/BJSCC.62.23

Masumi Itazaki, M. Kamitani

引用次数: 0

High-Valent Nonheme Iron Oxidants in Biology: Lessons from Synthetic Fe^IV=O Complexes. 生物学中的高价非血红素铁氧化剂:合成FeIV=O配合物的教训。

Bulletin of Japan Society of Coordination Chemistry Pub Date : 2013-11-01

Lawrence Que

引用次数: 0