Bulletin of Japan Society of Coordination Chemistry最新文献

{"title":"Recent Advances for Reaction Mechanisms of Metal-Catalyzed Activations of Carbon-Containing Bonds with the Aid of Density Functional Calculations","authors":"S. Mori","doi":"10.4019/BJSCC.72.15","DOIUrl":"https://doi.org/10.4019/BJSCC.72.15","url":null,"abstract":"アルキル基やアリール基のクロスカップリング反応 は、炭素―水素、炭素―炭素、炭素―ヘテロ原子結合の 開裂により、異なる炭素置換基を結合させる反応である。 玉尾および熊田のグループおよび R. Corriuらがそれぞれ 独立に、ハロゲン化アルケニルあるいはハロゲン化アリ ールと Grignard試薬を用いて Ni(II)触媒存在下でのクロ スカップリング反応を報告した 。その後、有機ハロ ゲン化物と有機ホウ素化合物からの Pd触媒存在下にお けるクロスカップリング反応である鈴木―宮浦カップリ ング反応 、ハロゲン化アリールあるいはハロゲン化ビ ニルと末端アルケンからスチレン誘導体をパラジウム触 媒存在下で合成する溝呂木―Heck反応 、有機ハロゲ ン化物と有機亜鉛試薬 (有機アルミニウム試薬あるいは 有機ジルコニウム試薬を用いてもよい )を Niあるいは Pd触媒存在下で用いて反応させる根岸カップリング 8−10) など、多くのカップリング反応が開発され、工業的にも 応用されている。鈴木―宮浦カップリング反応および溝 呂木―Heck反応のメカニズムの実験および DFT法によ る解明については、総説等が報告されている 。これ らのカップリング反応の基質としてハロゲン化物など脱 離しやすい官能基が結合した有機化合物が用いられてい ることが多いが、生成するハロゲン化物の除去などの操 作が必要であり、環境負荷をいかに小さくするかの課題 が残っている 。 有機合成の分野では、複雑な骨格を持つ有機化合物の 合成において、炭素―炭素結合生成反応が非常に重要で あるが、近年、金属触媒による炭素―水素結合、炭素― 炭素結合や炭素―ヘテロ原子結合を始めとした不活性結 合の活性化反応が開発されている 。炭素―水素結合 活性化の例は多くみられるが、炭素―炭素結合や炭素― ヘテロ原子結合の活性化については報告例が少なく、有 機合成化学上さらにチャレンジングな課題となってい る。この反応は、原子経済的にも原子効率的にも最近注 目されている。Fig. 1に示すように、炭素―炭素結合や 炭素―ヘテロ原子結合(O,N)の結合エネルギーは、85 kcal/molよりも大きくなり、ブロモベンゼンの炭素−臭 素結合エネルギーよりも大きい 。","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2018-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.72.15","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47773888","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":"Exotic Functions of Flexible Coordination Polymer Crystals","authors":"Hiroshi Sato","doi":"10.4019/BJSCC.71.30","DOIUrl":"https://doi.org/10.4019/BJSCC.71.30","url":null,"abstract":"ナノメートルサイズの細孔を無数にもつ多孔性物質 は、ガス分子などの小分子を効率よく分離したり、除去 したりする機能性物質として古くから私たちの身の回り で活躍している材料である。金属イオンと有機配位子を 組み合わせて合成される「多孔性金属錯体(PCP: Porous Coordination Polymer)」または「金属−有機構造体(MOF: Metal–Organic Framework)」と呼ばれる多孔性物質の開 発においては、配位結合の多様性を活かし、分子レベル で細孔の大きさや形状、化学的性質を様々に設計し合成 できるため、加速度的に研究開発が進んでいる。PCP/ MOFが他の物質と比較してユニークな点は、結晶性で ありながら、環境に応じて柔軟にそれらの構造を変化さ せる点である 。PCP/MOFに合理的に構造柔軟性を導 入する代表的な手法を Fig.1に示した。「固さ」と「柔 らかさ」が協奏的に働くユニークな細孔機能材料の合成 と機能、メカニズム解明について筆者らは研究を進めて きており、現在までいくつかの興味ある結果を得ている。 ここでは、結晶材料の面白さに取りつかれる中で、筆者 らが幸運にも発見に至った事例をもとに固くも柔らかい 多孔性金属錯体結晶が示す特異機能をご紹介したい。","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2018-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42586366","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":"Metal coordination as a template strategy to make resilient woven materials","authors":"Yuzhong Liu, O. Yaghi","doi":"10.4019/BJSCC.71.12","DOIUrl":"https://doi.org/10.4019/BJSCC.71.12","url":null,"abstract":"Metal coordination has been used extensively as a template strategy in the field of supramolecular chemistry. Preorganization of molecular components into a desirable orientation by metal complexation has allowed for the designed synthesis of interlocking molecules in high yields. Synthetic chemists have since learned to intertwine discrete molecular entities into entangled architectures with increasing complexity limited only by imagination. This template strategy has recently been implemented in the making woven extended structures. By linking building units that contain a metal complex core, twoand three-dimensional (2D and 3D) frameworks can be constructed where long threads of covalently linked molecules that are interwoven at regular intervals and templated by the metal ions. Upon demetalation, the threads have high degrees of freedom for spatial deviation to take place between them while preserving the overall structure, endowing the material with exceptional mechanical properties and dynamics.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2018-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.71.12","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43018360","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":"Creation of Porous Functional Materials based on Self-organization of Multinuclear Metallomacrocycles","authors":"S. Tashiro","doi":"10.4019/BJSCC.71.39","DOIUrl":"https://doi.org/10.4019/BJSCC.71.39","url":null,"abstract":"錯体化学を基盤とした応用研究における代表例の一つ として、Metal–Organic Framework (MOF) などの多孔性 配位高分子をはじめとした多孔性結晶材料の開発と機 能化が挙げられる 。これら多孔性結晶の主な用途は、 物質貯蔵や混合物分離、重合反応、触媒などであり、最 近では包接分子の構造解析手法としても活用されはじめ ているが、これらの機能の根幹は言うまでもなく結晶細 孔内への分子の包接である。すなわち、多孔性結晶の機 能設計や性能向上を図るためには、結晶細孔内での分子 包接・配列を精密に設計・制御することが極めて重要で ある。 そのためのアプローチの一つとして、分子認識能を有 するホスト化合物を構成要素として多孔性結晶を作成す ることができれば、細孔内での分子包接・配列をあらか じめプログラムすることが可能となり、その設計性およ び包接効率を格段に向上させることができる 。すな わち、環状ないしはケージ状ホスト化合物を構成要素と した多孔性結晶を合成できれば、それらの構成要素が本 来持つ高い分子認識能を結晶細孔内にそのまま組み込む ことが可能となる(Fig. 1)。例えば配位高分子では、柱 となる有機配位子にクラウンエーテル やピラーアレ ーン などの環状ホスト化合物を組み込んだ多孔性結 晶が合成されている。また、環状ホスト化合物自身を配 位高分子の柱そのものとして活用することもでき、その 代表例の一つは Stoddartらによって開発された CD-MOF であり、これはシクロデキストリン(CD)とアルカリ 金属イオンからなる多孔性配位高分子である。興味深い ことに、ある種の CD-MOFは食用原料のみから合成す ることも可能であり、Edible MOFとしても知られてい In this account, a new method for the creation of porous functional materials based on the self-organization of metallomacrocycles is described. For instance, the authors have developed a new series of porous molecular crystals, metal– macrocycle frameworks (MMFs), through crystallization of Pd3-macrocycles. It was also found that MMFs with multiple binding pockets on the pore surface served as excellent host frameworks for precise molecular arrangement, chiral recognition, sizespecific catalytic reaction, and in situ observation of a molecular adsorption process. In addition, the one-dimensional assembly of metallomacrocycles is also described as another approach for the construction of metal-modified pores and various metal arrays. This method is therefore one of the promising ways to develop unique porous materials such as highly efficient and selective catalysts based on the precise arrangement of guest compounds and metal ions in the pores.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2018-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.71.39","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48601991","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":"Coordination Chemistry Pioneered by Bridging Si- and Ge-Ligands","authors":"K. Osakada","doi":"10.4019/BJSCC.71.3","DOIUrl":"https://doi.org/10.4019/BJSCC.71.3","url":null,"abstract":"Transition metal complexes, having the coordination bonds with strong covalent-bond characters, undergo various bond-forming reactions, similar to the organo-transition metal complexes with a metal-carbon s -bond. This article reviews recent studies by the author and his co-workers on the multinuclear complexes of group 10 transition metal complexes having bridging Si- and Ge-ligands. Triangular triplatinum(0) complexes having three bridging diarylsilylene ligands are newly prepared, and undergo skeletal rearrangement on addition of alkynes. The complex with SiPh 2 ligands catalyzes hydrosilylation of aromatic aldehydes and ketones with H 2 SiPh 2 . Detailed studies on the dipalladium and diplatinum complexes with bridging Si- and Ge-ligands revealed unique chemical properties, such as activation of the Si–H bond of the ligand as well as bond forming reactions of the bridging germylene with germyl ligands. Tetra-, penta-, hexa-, and octa-nuclear Pd and Pt complexes with the bridging silylene and germylene ligands are obtained from heating a mixture of the metal-phosphine complexes, precursor of the Si- and Ge-ligands, and scavenger of the auxiliary ligands. Thus formed complexes react with metal halides and with the Si- and Ge-compounds to produce new multinuclear transition metal complexes. The reactions occur reversibly because of kinetic lability of the multinuclear complexes with the bridging Si- and Ge-ligands.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2018-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.71.3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48346262","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":"Development of approximate spin projection method and its application for elucidation of electronic structures, molecular structures and physical properties of polynuclear metal complexes","authors":"Y. Kitagawa, Toru Saito, K. Yamaguchi","doi":"10.4019/bjscc.71.57","DOIUrl":"https://doi.org/10.4019/bjscc.71.57","url":null,"abstract":"近年の量子化学理論および計算機の発達は、実在する 比較的大きな分子の第一原理計算を可能とした。また、 第一原理計算に関する商用ソフトウェアの普及は、広く 研究者に量子化学計算を実行する環境を提供したことも あり、様々な分子の電子状態、構造、そして特性が第一 原理的に求められるようになってきた。今や理論計算は 化学分野において、合成、測定に次ぐ第三のアプローチ としての地位を確立しつつある。実際、多くの化学雑誌 において、第一原理計算の結果を含んだ論文を目にする ようになった。錯体分野に関しても第一原理計算による 理論的解釈が行われるようになってきた。 錯体の電 子状態の特徴の一つには、主として d軌道による擬縮退 したフロンティア軌道と、そこに存在する金属イオンの 不対電子(=電子スピン)の存在があげられる。このよ うな、局在スピンサイトを有する系を一般的に開殻系と 呼ぶが、特に複核錯体では、錯体中の金属イオンが複数 の局在スピンサイトとなるため、多様なスピン状態を生 み出す。 この開殻性を有した物質群は、物性物理の分 野では強相関電子系とも呼ばれ、スピン・軌道・フォノ ンなどが絡み合い、例えば磁性、伝導性、光物性など 多様な物性を発現する。 また近年注目を集めている、 PSII光合成活性中心のMnクラスター やフェレドキ シンなどの電子伝達タンパク質に含まれる鉄-硫黄ク ラスター なども強相関電子系であり、生体は巧みに この性質を利用しながら反応を行なっていることも明ら かになりつつある。従って、第一原理計算を用い、これ らの分子構造・電子(スピン)状態そして物性発現機構 の関係性をミクロな視点から明らかにすることができれ ば、そこから機能性分子の設計原理を導出することも可 能となる。このように、第一原理計算による錯体の特性 解明、そして機能性分子の理論設計は今後ますます進展 することが予想される。しかしながら後述するように、 A broken-symmetry (BS) method is now widely used for systems that involve (quasi) degenerate frontier orbitals because of their lower cost of computations. The BS method splits up-spin and down-spin electrons into two different spatial orbitals. Within the BS method, therefore, a singlet spin state of the degenerate system is expressed as a spinpolarized state e.g. a singlet diradical. However the spin-polarized wavefunction suffers from a serious problem called a spin contamination error. An approximate spin projection (AP) method can eliminate the error from the BS solution by assuming the Heisenberg model, and one can obtain molecular energies and its derivatives without the error. In this accounts, we illustrate a theoretical background of the BS and AP methods, starting from a bond dissociation of the simplest H2 molecule. And we also show some examples of its application especially for Cr(II)2 complex that is a typical spin-polarized system with a multiple bond.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2018-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/bjscc.71.57","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70514979","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":"Photo- and electrocatalytic H2 evolution with cobalt oxime complexes","authors":"Janina Willkomm, E. Reisner","doi":"10.4019/BJSCC.71.18","DOIUrl":"https://doi.org/10.4019/BJSCC.71.18","url":null,"abstract":"41 in of electro-and photocatalytic integrate materials devices for (light-driven) H 2 evolution. 42–47 the application cobalt oxime complexes as catalysts in such systems reviewed. Converting sunlight into storable chemical energy carriers, such as dihydrogen (H 2 ), through light-driven splitting of water is a widely studied approach to secure future energy supplies and sustainability. Molecular complexes based on inexpensive and earth-abundant 3d transition metals have been extensively explored as catalysts for the reduction of water to H 2 . Among these, cobalt complexes with an oxime functionality ( i.e., cobaloxime and cobalt diimine-dioxime) efficiently reduce protons in pure water with low to moderate overpotentials, and they have been shown to remain active under aerobic conditions. Based on their simple and straightforward synthesis in addition to their excellent electrochemical properties, they are often applied as the first-choice catalyst when testing new materials or introducing new concepts for H 2 evolution. In this review, their basic electrochemical and electrocatalytic properties as well as mechanistic investigations will be summarized, followed by an overview of their application in photocatalysis. Finally, their integration with (nano)materials for (photo)electrocatalytic H 2 evolution is presented and discussed.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2018-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.71.18","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47212191","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 significance of the “distorted chair” topology of the Mn cluster for oxygen evolution in photosynthesis","authors":"H. Isobe","doi":"10.4019/BJSCC.70.2","DOIUrl":"https://doi.org/10.4019/BJSCC.70.2","url":null,"abstract":"自然界におけるほとんどすべての生命活動は、恒常的 に得られる太陽光エネルギーを利用して大気中の二酸化 炭素から生物が利用可能な有機物を生産する光合成に依 存している。光合成を生命と地球の共進化の視点から眺 めて特筆すべき点は、藻類や緑色植物など多くの光合成 を行う生物が地球上に豊富に存在する水を電子の供給源 として用いる高度な仕組みを獲得したことである。副産 物として放出された大量の酸素は長い年月をかけて海中 や大気に蓄積され、生物に有害な紫外線を吸収するオゾ ン層が形成された。さらに、猛毒である酸素への耐性と 大きなエネルギー変化を伴う酸素循環を利用した呼吸機 能を生物が獲得することで、太陽光という無尽蔵のエネ ルギーを利用して有限な炭素を無機的環境と生物界の間 で無限に循環させることができる高効率で持続可能なエ ネルギー変換の仕組みが確立された。酸素の高い酸化力 は、膨大な数の有機化合物を代謝・生合成する酵素群の 分子進化と生理機能の多様化をもたらし、生物進化を推 進する原動力となった。光合成が生物界で水を分解して 酸素を発生させることができる唯一の反応系である事実 を考えれば、そのメカニズムを理解することは、学術的 意義に留まらず、地球温暖化や化石燃料枯渇に伴う環境・ エネルギー問題の解決を考える上で極めて重要な研究課 題になっていることは論を俟たない。 光合成の初期過程である光エネルギーから化学エネル ギーへの変換は、光の吸収と励起によって誘起される電 荷分離とそれに続く電子移動と ATP合成からなる膨大 な数の反応の連鎖である。一連の電子伝達反応の酸化側 末端で、光合成に必要な電子を供給する重要な役割を担 っているのが光化学系 II(Photosystem II、PSII)と呼ば れる膜タンパク質複合体である 。そのため、PSIIには 一定の位置と配向で固定された電子伝達コファクターと バルクの水分子をタンパク質内部に導く(あるいはプロ トンや酸素を排出する)輸送トンネル構造があり、周 囲には吸収した光エネルギーを PSII内部の特別な環境 に置かれたクロロフィル a二量体(反応中心 P680)に 集約するためのアンテナ系が高度に発達している 。輸 送トンネルの先には、酸素発生複合体(oxygen-evolving complex、OEC)と呼ばれる活性部位があり、水の分解・ 酸素発生反応(2H2O→ O2 + 4H + 4e)は OEC内のMn 酸化物クラスターの触媒作用によって起こる 。上で 述べたように、シアノバクテリアによる酸素発生を伴う This account describes a current summary of our computational studies intended to elucidate the mechanism underlying water oxidation by the tetranuclear Mn cluster in the oxygen-evolving complex of photosystem II, the most fundamental bioenergetic process required for the maintenance of life. We focus herein on several important findings about the relatively high oxidation (S2 and S3) states of the cluster that involve three or four Mn IV and one or no Mn ions. The presentation is designed to highlight how the cluster stores the oxidizing power, binds substrate water molecules, and activates them. We discuss the fundamental importance of the cooperative effects of multiple Jahn–Teller axes on Mn ions, which inevitably deform the cluster structure in such a direction as to promote substrate binding during S2 → S3 transition and O–O bond formation in the S3 state. Our interpretation is that the “distorted chair” topology of the cluster is the heart of efficient catalysis for oxygen evolution, and the presentation attempts to reflect this view.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":"70 1","pages":"2-13"},"PeriodicalIF":0.0,"publicationDate":"2017-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.70.2","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46158614","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":"Metal-Based Molecular Functional Materials - From Discrete Metal Complexes to Supramolecular Assembly, Nanostructures and Functions","authors":"V. Yam","doi":"10.4019/BJSCC.69.21","DOIUrl":"https://doi.org/10.4019/BJSCC.69.21","url":null,"abstract":"The continuous search for smart and advanced materials with enhanced photofunctional features has attracted a world-wide interest and resulted in great efforts towards the investigations and developments of molecular-based functional materials. It has been known that the chemical and physical properties of various organic moieties can be influenced by and correlated to their molecular structures. As a result of this, the coordination chemistry of transition metal complexes, through the utilization of various transition metal centers and their incorporation into the organic moieties with diverse combinations, has been found to give rise to superior advantages of greater versatility of molecular design and thus leading to more in-depth understanding for the exploration of photofunctional materials with tunable photophysical and excited state properties. In the past few decades, the photophysics and photochemistry of transition metal complexes have drawn inter-disciplinary attention and resulted in significant impact towards materials and energy research, especially with the detailed investigations on the class of ruthenium(II) polypyridine complexes with the characteristic metal-to-ligand charge transfer (MLCT) excited state, arising from their rich photoredox and photoluminescence properties and good stability. These have provided insights into the exploration of molecular-based functional materials with concepts of supramolecular photochemistry. In addition to the ruthenium(II) polypyridine system, researchers also investigated the photophysics and photochemistry of iridium(III) system because of their synthetic versatility, high photoand thermal stabilities with tunable emission color and thus can be applied as triplet emitters and phosphorescent dopants in organic light emitting devices (OLEDs). In addition, lots of efforts have also been devoted into the exploration of new classes of luminescent transition metalligand chromophores and their application in materials chemistry and science by understanding and rationalization of their excited state properties. By the utilization of ligands with versatile structural and electronic properties, the excited state properties of transition metal complexes can be fine-tuned and controlled. For example, the incorporation of strong s-donating ligands has been found to cause drastic luminescence enhancement of some classes of transition metal complexes because of the destabilization of non-emissive d–d ligand field excited states. Compared to the d ruthenium(II) and iridium(III) complexes with octahedral geometry, the square-planar d transition metal complexes with coordinationunsaturated nature has been found to exhibit intriguing spectroscopic and luminescence properties due to their unique tendency to form non-covalent metal···metal interactions. Platinum(II) complexes have been extensively explored in previous years due to their intriguing chromphoric and aggregation properties. The introduction of sup","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":"69 1","pages":"21-28"},"PeriodicalIF":0.0,"publicationDate":"2017-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.69.21","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48024436","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 Organization of Bioorganometallic Complexes Composed of Nucleobases","authors":"T. Moriuchi","doi":"10.4019/BJSCC.70.22","DOIUrl":"https://doi.org/10.4019/BJSCC.70.22","url":null,"abstract":"In this account, recent advances in the design of bioorganometallic complexes by the conjugation of organometallic complexes with nucleobases are focused on to exhibit specific properties based on functional organization. A guanosine-based Au(I) bioorganometallic complex is demonstrated to serve as the reliable G-octamer scaffold via self-organization, showing a switchable emission based on aurophilic Au(I)-Au(I) interaction. The formation of the empty quartet, octamer, and polymeric columnar aggregate is able to be controlled by the amount of potassium ion. The tuning of the emission properties of the bioorganometallic platinum(II) complexes bearing a uracil moiety is also achieved by changing the direction of hydrogen bonding sites and the molecular scaffold having complementary hydrogen bonding sites for the uracil moiety. The semirigid bridging diphosphine ligand is performed to be a key factor in the arrangement of the phosphorus atoms on the same side to induce intramolecular Au(I)-Au(I) interaction, wherein R - and S -enantiomers based on Au(I)-Au(I) axis exist. It is noteworthy that the chirality of Au(I)-Au(I) axis is induced by the utilization of ( R )-BINAP as the axially chiral bridging diphosphine ligand. Another interesting feature of bioorganometallic complexes is their strong tendency to self-assemble through intermolecular hydrogen bonds between their nucleobase moieties.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":"70 1","pages":"22-31"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.4019/BJSCC.70.22","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70514830","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}