{"created":"2022-01-27T08:05:33.260611+00:00","id":2004451,"links":{},"metadata":{"_buckets":{"deposit":"acb4f57a-ed7e-4e90-a8a5-e3bbcdf2dcbb"},"_deposit":{"id":"2004451","owners":[1],"pid":{"revision_id":0,"type":"depid","value":"2004451"},"status":"published"},"_oai":{"id":"oai:u-ryukyu.repo.nii.ac.jp:02004451","sets":["1642838403123","1642838403551:1642838406414"]},"author_link":[],"item_1617186331708":{"attribute_name":"Title","attribute_value_mlt":[{"subitem_1551255647225":"ビスマスイオンを母核とするp、d、fブロック : 元素とのヘテロ金属多核錯体の合成","subitem_1551255648112":"ja"},{"subitem_1551255647225":"Synthesis of polynuclear hetero-metal complexes of Bi-p, -d, and -f block elements","subitem_1551255648112":"en"}]},"item_1617186419668":{"attribute_name":"Creator","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"安里, 英治","creatorNameLang":"ja"}]},{"creatorNames":[{"creatorName":"Asato, Eiji","creatorNameLang":"en"}]}]},"item_1617186476635":{"attribute_name":"Access Rights","attribute_value_mlt":[{"subitem_1522299639480":"open access","subitem_1600958577026":"http://purl.org/coar/access_right/c_abf2"}]},"item_1617186609386":{"attribute_name":"Subject","attribute_value_mlt":[{"subitem_1522299896455":"ja","subitem_1522300014469":"Other","subitem_1523261968819":"ヘテロ金属多核錯体"},{"subitem_1522299896455":"ja","subitem_1522300014469":"Other","subitem_1523261968819":"ビスマス"},{"subitem_1522299896455":"ja","subitem_1522300014469":"Other","subitem_1523261968819":"複合酸化物"},{"subitem_1522299896455":"ja","subitem_1522300014469":"Other","subitem_1523261968819":"X線結晶構造解析"},{"subitem_1522299896455":"ja","subitem_1522300014469":"Other","subitem_1523261968819":"粉末X線回折"},{"subitem_1522299896455":"ja","subitem_1522300014469":"Other","subitem_1523261968819":"熱分解"},{"subitem_1522299896455":"ja","subitem_1522300014469":"Other","subitem_1523261968819":"クラスター錯体"},{"subitem_1522299896455":"en","subitem_1522300014469":"Other","subitem_1523261968819":"Polynuclear hetero-metal comnlex"},{"subitem_1522299896455":"en","subitem_1522300014469":"Other","subitem_1523261968819":"Bismuth complex"},{"subitem_1522299896455":"en","subitem_1522300014469":"Other","subitem_1523261968819":"Polymetallic oxide"},{"subitem_1522299896455":"en","subitem_1522300014469":"Other","subitem_1523261968819":"X-ray crystal structure analysis"},{"subitem_1522299896455":"en","subitem_1522300014469":"Other","subitem_1523261968819":"Powder X-ray diffraction"},{"subitem_1522299896455":"en","subitem_1522300014469":"Other","subitem_1523261968819":"Thermal decomposition"},{"subitem_1522299896455":"en","subitem_1522300014469":"Other","subitem_1523261968819":"Cluster comniex"}]},"item_1617186626617":{"attribute_name":"Description","attribute_value_mlt":[{"subitem_description":"科研費番号: 12640543","subitem_description_type":"Other"},{"subitem_description":"平成12～14年度科学研究費補助金(基盤研究(C)(2))研究成果報告書","subitem_description_type":"Other"},{"subitem_description":"（研究概要）フエノキソ架橋型二核化配位子に焦点を絞り、「ビスマスイオン認識ユニット」と「異種金属認識ユニット」を組み込んだ新しい非対称型配位子を合成した。この配位子にBiを挿入したメタラサイクル型Bi単核錯体を出発原料に用いる事で、多様なBi-dブロック二核系[Bi- V(IV)=O,-Cr(III),-Mn(III),-Fe(III),-Co(III),-Ni(II),-Cu(II)]、Bi-pブロック二核系錯体[Bi-Zn(II),-Al(III)]が得られる事を明らかにした。ビスマス錯体の多くは水で速やかに加水分解を起こし、不溶性のビスムチル塩 (BiO^+)を生成するが、この二核化キレート多座配位子から得られるBi(III)-異種金属系錯体は加水分解を起こさず、NMR測定からも水中で安定に骨格を保つ事が確認された。\\nBi(III)-Cu(II)系錯体の熱分解過程をTGAより解析した結果、300℃という比較的低温で配位子が完全に分解し、600℃以上ではBiは全て複合酸化物になる事がXRD法により確認され、この方法が均一性の高い複合酸化物を得るのに有効な手法である事を提案した。\\n2-ヒドロキシルエチルN-イミノジ酢酸(H_3heida)を用いて、(NH_4)[Bi_3(heida)_3(OH)]・ 6H_2・MeOHを合成し、X線構造解析によりμ-3-OHユニットを有するBi三核クラスターであることを明らかにした。この錯体は3つのBiイオンが不完全キュバン骨格を形成しており、その金属欠損部位にNH_4^+イオンが捕捉されている。NH_4^+イオンのK^+に置換したカリウム誘導体の合成に成功し、各種分光学的測定から、先のNH_4誘導体と同様な異種金属キュバン骨格の四核錯体であることを明らかにし、この方法がBi_3M型異種金属キュバンクラスターの合成に有効である事を提案した。","subitem_description_type":"Other"},{"subitem_description":"In order to establish rational preparative method to create Bi-based hetero-metal dinuclear complexes, a new phenol-based ligand H_6L was prepared. Reaction of H_6L with Bi(N0_3)_3・5H_2O afforded mononuclear Bi complex [Bi(H_3L)]・H_2O, where Bi atom is trapped into \"Bi-recognition site\" embedded in the ligand.This complex still contains an empty coordination site for a second metal ion, and indeed reacts with a variety of d-block and p-block elements.Successfully isolated dinuclear complexes are as follows ; Bi-V(IV)=O, -Cr(III), -Mn(III), -Fe(III), -Co(llI), -Ni(II), -Cu(II), -Zn(II), and -AI(III).As potential precursors for polymetallic oxides, thermal decomposition process of these complexes was examined using TGA analysis and XRD measurement.As a representative case, Bi-Cu hetero-nuclear complex loses all of its organic ingredients at around 300℃ to become a mixture of Bi_2CuO_4, Bi_2O_3, and CuO.The latter two ingredients further react each other at higher temperatures, and finally causing disappearance of Bi_2O_3 ingredient above 600℃.\\nAnother approach to hetero-metal clusters was also examined.A commercially available ligand N-2-hydroxyethyl)iminodiacetic acid(H_3heida)reacts with Bi ion in a mixed solvent of aqueous ammonia and methanol to give trinuclear Bi complex (NH_4)[Bi_3(heida)_3(OH)]・6H_2O・MeOH.Its structure is characterized as an incomplete cuban[Bi_3(μ-O_<alkoxo>alkoxo)_3(μ_3-OH)], where the three Bi atoms are bridged by the hydroxide ion (μ_3-OH) and adjacent Bi pairs are further bridged by the alkoxo oxygen of heida^<3->.The metal deficient position of the pre-cubane is occupied by NH^+_4 through hydrogen bonding toward the three bridging alkoxo oxygens.The NH^+_4 can be easily replaced by K^+ to form a mixed cluster [Bi_3K(μ_3-O)_4].This finding suggests that the trinuclear pre-cubane may function as a potential precursor for the mixed clusters of [Bi_3M(μ_3-O)_4] type, where M is d-block and p-block elements, while no such mixed metal clusters have been obtained yet.","subitem_description_type":"Other"},{"subitem_description":"未公開：P.38以降（別刷論文のため）","subitem_description_type":"Other"},{"subitem_description":"研究報告書","subitem_description_type":"Other"}]},"item_1617186643794":{"attribute_name":"Publisher","attribute_value_mlt":[{"subitem_1522300295150":"ja","subitem_1522300316516":"安里英治"}]},"item_1617186702042":{"attribute_name":"Language","attribute_value_mlt":[{"subitem_1551255818386":"jpn"}]},"item_1617186783814":{"attribute_name":"Identifier","attribute_value_mlt":[{"subitem_identifier_type":"HDL","subitem_identifier_uri":"http://hdl.handle.net/20.500.12000/9267"}]},"item_1617186920753":{"attribute_name":"Source Identifier","attribute_value_mlt":[{"subitem_1522646500366":"NCID","subitem_1522646572813":"BA74249814"}]},"item_1617187056579":{"attribute_name":"Bibliographic Information","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2004-03","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"none"}]},"item_1617258105262":{"attribute_name":"Resource Type","attribute_value_mlt":[{"resourcetype":"research report","resourceuri":"http://purl.org/coar/resource_type/c_18ws"}]},"item_1617265215918":{"attribute_name":"Version Type","attribute_value_mlt":[{"subitem_1522305645492":"VoR","subitem_1600292170262":"http://purl.org/coar/version/c_970fb48d4fbd8a85"}]},"item_1617605131499":{"attribute_name":"File","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_access","filename":"12640543.pdf","mimetype":"application/pdf","url":{"objectType":"fulltext","url":"https://u-ryukyu.repo.nii.ac.jp/record/2004451/files/12640543.pdf"},"version_id":"414638d5-ddc8-4aa6-9284-8ca75b9cefa6"}]},"item_title":"ビスマスイオンを母核とするp、d、fブロック : 元素とのヘテロ金属多核錯体の合成","item_type_id":"15","owner":"1","path":["1642838403123","1642838406414"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2009-03-17"},"publish_date":"2009-03-17","publish_status":"0","recid":"2004451","relation_version_is_last":true,"title":["ビスマスイオンを母核とするp、d、fブロック : 元素とのヘテロ金属多核錯体の合成"],"weko_creator_id":"1","weko_shared_id":-1},"updated":"2022-10-31T01:57:57.132300+00:00"}