{"created":"2021-03-01T06:22:19.516620+00:00","id":5623,"links":{},"metadata":{"_buckets":{"deposit":"2c61df91-89bc-4432-b9fe-485327966a95"},"_deposit":{"id":"5623","owners":[],"pid":{"revision_id":0,"type":"depid","value":"5623"},"status":"published"},"_oai":{"id":"oai:repository.dl.itc.u-tokyo.ac.jp:00005623","sets":["75:159:399","9:233:280"]},"item_7_alternative_title_1":{"attribute_name":"その他のタイトル","attribute_value_mlt":[{"subitem_alternative_title":"Construction of supramolecular structures by assembling planar mononuclear metal complexes"}]},"item_7_biblio_info_7":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2009-03-23","bibliographicIssueDateType":"Issued"},"bibliographic_titles":[{}]}]},"item_7_date_granted_25":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"2009-03-23"}]},"item_7_degree_grantor_23":{"attribute_name":"学位授与機関","attribute_value_mlt":[{"subitem_degreegrantor":[{"subitem_degreegrantor_name":"University of Tokyo (東京大学)"}]}]},"item_7_degree_name_20":{"attribute_name":"学位名","attribute_value_mlt":[{"subitem_degreename":"博士(理学)"}]},"item_7_description_5":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"本研究は、単核平面型金属錯体を様々な分子間相互作用により連結、集積する事によって配位高分子、分子性結晶、ゲル等の超分子集合体を構築する事を目的に行われた。その過程において、この合成手法が目的とする超分子集合体の構築に有効であること、溶液中のみならず固相中でも超分子集合体構築が可能でその構造変化も起こりうること、さらに、ひとつを見れば剛直で可動性に乏しい金属錯体も、その超分子集合体は構造柔軟性を持ち、それに由来する様々な特性を発揮しうる事が見出された。まず、配位高分子合成においては、固定された直線型配位構造、配位子の修飾や交換による化学性の調節、有機溶媒への可溶性、電気的に中性等の利点を考え平面型金属錯体[CoII(β-diketonato)2]を選択し、これと種々の配位子との自己集合を溶液中で試みた。その結果、2D(6,3)net 型配位高分子の合成とそのスタッキング様式の制御、配位子の配座制御、１次元配位高分子全体のねじれ制御によるキラリティー誘起に成功した。次に、通常は液相で行われる金属イオンと配位子の自己集合を固相で誘起する事を試み、3-cyano-pentane-2,4-dioneとM(OAc)2·nH2O（M = MnII, FeII, CoII, NiII, CuII, ZnII, CdII）の固体混合物から、固相反応によって配位高分子が構築できる事を見い出した。また、固相における、単核錯体と配位高分子間の可逆的な構造変換や、配位高分子の構造変換が進行する事例も見出した。これは通常は剛直と考えられている配位高分子が柔軟性を、固相においてさえも、持ちうる事を示している。さらに、より柔軟な金属錯体集合体の構築を目指し、平面構造、両親媒性構造、５配位構造の特徴を持つ [CoCl2(bppp)]を合成し、その集積により分子性結晶とゲルを得た。分子性結晶内にはπ-π相互作用によるスタック構造が形成されており、これは、アセトン蒸気中でアセトン分子を吸収する構造柔軟性を示す。同時に、配位構造の変化に起因する、緑からピンクへの色変化（ベイポクロミック挙動）を示した。ゲル化は、[CoCl2(bppp)]のメタノール溶液に水を添加した際に見られた。ゲル状態では[CoCl2(bppp)]と[Co(bppp)2]2+が混合していると考えられるが、類似錯体との比較検討から、[CoCl2(bppp)]が結晶内で見せるような分子間相互作用により超分子的に集積し、それがゲルの3 次元網目骨格を形成していると考えられる。また、比較的剛直な3,2’:6’,3’’-terpyridine 骨格を複数個有するオリゴピリジンがCoII イオンあるいはAgI イオンとの組み合わせにおいてゲル化する事も見出した。このように剛直な金属錯体ビルディングブロックも、外場応答性を示す分子性結晶やゲルといった柔軟な超分子集合体の構築に有用である事が明らかとなった。これらの知見は、金属錯体の超分子集合体における新たな一面を引き出したとともに、この分野の今後の発展に寄与するものである。","subitem_description_type":"Abstract"},{"subitem_description":"By using planar mononuclear metal complexes as a building block, new supramolecular assemblies such as coordination polymers, molecular crystals and gels have been synthesized. In the course of this study, the followings have been clarified: this synthetic approach is useful for constructing aimed coordination　polymers; the formation of supramolecular assemblies and their structural transformations are possible even in a solid-state phase; rigid metal complexes can assemble to form a supramolecular assembly having a flexible and soft structure and some functions coming from the structural flexibility. In the synthesis of coordination polymers, [Co(β-diketonato)2] was chosen as a building block due to its several merits such as a fixed linear coordination geometry, high solubility to common organic solvents and neutral electric charge. Moreover, its Lewis acidity and stereo-chemical properties can be tuned by modification and exchange of the β-diketonate ligand. In combinations of [Co(β-diketonato)2] and various organic ligands, formation of new 2D coordination polymers, control of stacking manner of the 2D polymers, conformational control of the organic ligands, control of twisting of a 1D coordination polymer and induction of its helical chirality were achieved. As a next subject, the self-assembly process of metal ions and ligands in a solid-state phase was investigated in the combination of 3-cyano-pentane-2,4-dione and metal acetates. In many cases, such a process proceeds in a solution so that searching the possibility of self-assembly in the solid-state phase is challenging. As a result, using grinding/annealing treatments the formation of mononuclear metal complexes and coordination polymers were achieved. Moreover, reversible structural conversion between mononuclear complexes and coordination polymers and one-way conversion of a coordination polymer to another in the solid state were confirmed. These results indicate that coordination polymers, which are usually considered to be rigid, are flexible and soft even in the solid-state phase. For constructing more flexible supramolecular assemblies, [CoCl2(bppp)], which has some structural characteristics such as a planar structure, an amphiphilic structure and a penta-coordination geometry, was newly synthesized. From [CoCl2(bppp)] two supramolecular structures, a molecular crystal and a gel, were obtained. In the molecular crystal, [CoCl2(bppp)] are stacked through π-π interactions. This molecular crystal absorbed acetone molecules on exposure to acetone vapor and changed its color from green to pink simultaneously. The gel formation occurred by adding water to a methanol solution of [CoCl2(bppp)]. The gel is likely to contain [Co(bppp)2]2+ besides [CoCl2(bppp)]. However, comparison with related complexes suggests that the 3D network forming the gel-state is formed by assembly of [CoCl2(bppp)] through supramolecular interactions observed in the molecular crystals. As another example, oligopyridines with multi 3,2’:6’,3”-terpyridine moieties were found to turn into gel through interactions with CoII and AgI ions. As shown above, several flexible supramolecular structures formed with rigid metal complex building blocks have been demonstrated. These findings give a new image to supramolecular assemblies of metal complexes and lead to further development of supramolecular chemistry.","subitem_description_type":"Abstract"}]},"item_7_dissertation_number_26":{"attribute_name":"学位授与番号","attribute_value_mlt":[{"subitem_dissertationnumber":"甲第24486号"}]},"item_7_full_name_3":{"attribute_name":"著者別名","attribute_value_mlt":[{"nameIdentifiers":[{"nameIdentifier":"11700","nameIdentifierScheme":"WEKO"}],"names":[{"name":"Yoshida, Jun"}]}]},"item_7_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.15083/00005614","subitem_identifier_reg_type":"JaLC"}]},"item_7_select_21":{"attribute_name":"学位","attribute_value_mlt":[{"subitem_select_item":"doctoral"}]},"item_7_text_22":{"attribute_name":"学位分野","attribute_value_mlt":[{"subitem_text_value":"Science (Rigaku)(理学)"}]},"item_7_text_24":{"attribute_name":"研究科・専攻","attribute_value_mlt":[{"subitem_text_value":"Department of Chemistry, Graduate School of Science (理学系研究科化学専攻)"}]},"item_7_text_27":{"attribute_name":"学位記番号","attribute_value_mlt":[{"subitem_text_value":"博理第5384号"}]},"item_7_text_4":{"attribute_name":"著者所属","attribute_value_mlt":[{"subitem_text_value":"東京大学大学院理学系研究科 化学専攻"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"吉田, 純"}],"nameIdentifiers":[{"nameIdentifier":"11699","nameIdentifierScheme":"WEKO"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2017-06-01"}],"displaytype":"detail","filename":"1235954205_13069.pdf","filesize":[{"value":"19.7 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"1235954205_13069.pdf","url":"https://repository.dl.itc.u-tokyo.ac.jp/record/5623/files/1235954205_13069.pdf"},"version_id":"05ed0bb1-fc9e-4f9d-85fb-f10bdc38782f"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"jpn"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"thesis","resourceuri":"http://purl.org/coar/resource_type/c_46ec"}]},"item_title":"平面構造を有する単核金属錯体の集積による超分子構造体の構築","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"平面構造を有する単核金属錯体の集積による超分子構造体の構築"}]},"item_type_id":"7","owner":"1","path":["280","399"],"pubdate":{"attribute_name":"公開日","attribute_value":"2014-02-24"},"publish_date":"2014-02-24","publish_status":"0","recid":"5623","relation_version_is_last":true,"title":["平面構造を有する単核金属錯体の集積による超分子構造体の構築"],"weko_creator_id":"1","weko_shared_id":null},"updated":"2022-12-19T03:47:12.500084+00:00"}