{"_buckets": {"deposit": "8a5e02bc-6c7a-4efc-b502-1aaf313b4d6f"}, "_deposit": {"created_by": 21, "id": "1651", "owners": [21], "pid": {"revision_id": 0, "type": "depid", "value": "1651"}, "status": "published"}, "_oai": {"id": "oai:ir.soken.ac.jp:00001651", "sets": ["9"]}, "author_link": ["0", "0", "0"], "item_1_biblio_info_21": {"attribute_name": "書誌情報（ソート用）", "attribute_value_mlt": [{"bibliographicIssueDates": {"bibliographicIssueDate": "2010-03-24", "bibliographicIssueDateType": "Issued"}, "bibliographic_titles": [{}]}]}, "item_1_creator_2": {"attribute_name": "著者名", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "小田, 雅文"}], "nameIdentifiers": [{"nameIdentifier": "0", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_creator_3": {"attribute_name": "フリガナ", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "オダ, マサフミ"}], "nameIdentifiers": [{"nameIdentifier": "0", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_date_granted_11": {"attribute_name": "学位授与年月日", "attribute_value_mlt": [{"subitem_dategranted": "2010-03-24"}]}, "item_1_degree_grantor_5": {"attribute_name": "学位授与機関", "attribute_value_mlt": [{"subitem_degreegrantor": [{"subitem_degreegrantor_name": "総合研究大学院大学"}]}]}, "item_1_degree_name_6": {"attribute_name": "学位名", "attribute_value_mlt": [{"subitem_degreename": "博士（理学）"}]}, "item_1_description_1": {"attribute_name": "ID", "attribute_value_mlt": [{"subitem_description": "2010009", "subitem_description_type": "Other"}]}, "item_1_description_12": {"attribute_name": "要旨", "attribute_value_mlt": [{"subitem_description": "　The supramolecular integration of porphyrin and its derivatives has attracted\u003cbr /\u003e to obtain well-defined porphyrin aggregates, not only covalent bonding but also metal\u003cbr /\u003e coordination, hydrogen-bonding and van der Waals interactions have been utilized\u003cbr /\u003e and the obtained integrated structures have been employed for applications in various\u003cbr /\u003e fields of materials science and technology.  I have focused on the supramolecules of\u003cbr /\u003e amphiphilic motives with rigid π-conjugated cores, which have been well employed to\u003cbr /\u003e obtain excellent optoelectronic properties associated with the characteristic\u003cbr /\u003e nanostructures.  In this study, I have developed an asymmetrically β-substituted\u003cbr /\u003e amphiphilic porphyrin, which is designed to be much planar and less bulky with an\u003cbr /\u003e aim to accomplish densely packed nanostructures and induce strong intermolecular\u003cbr /\u003e interactions between the metal centers.\u003cbr /\u003e　The triethyleneglycol(TEG)-tethered and alkyl-tethered dipyrromethanes have\u003cbr /\u003e been prepared, and then the synthesis of the target porphyrin has been accomplished\u003cbr /\u003e by the condensation reaction of these dipyrromethanes.  In contrast to the synthesis\u003cbr /\u003e of \u003ci\u003emeso\u003c/i\u003e-aryl-type porphyrin, that of asymmetrically substituted β-alkyl-type\u003cbr /\u003e porphyrin has not been well explored.  Several conditions were examined for the\u003cbr /\u003e condensation reaction of two different dipyrromethanes and finally, the target zinc\u003cbr /\u003e porphyrin was successfully obtained by condensation of TEG-tethered dipyrromethane\u003cbr /\u003e and an alkyl-tethered \u003ci\u003eα,α’\u003c/i\u003e-dipropylimino-dipyrromethane in refluxing cyclohexane in\u003cbr /\u003e the presence of Zn(OAc)\u003csmall\u003e2\u003c/small\u003e2H\u003csmall\u003e2\u003c/small\u003eO as a template.  In this procedure, an isomerization\u003cbr /\u003e reaction of porphyrin derivatives, so-called scrambling reaction, was suppressed under\u003cbr /\u003e lower reaction temperature or in less polar solvents by hampering the pathway of this\u003cbr /\u003e side-reaction.  For the optimized synthesis, 44.8 mg of the porphyrin mixture was\u003cbr /\u003e obtained in 18% yield and the ratio of the target compound and the isomer\u003cbr /\u003e (isomer/target) was 0.03.  The isolation of the target porphyrin 1-Zn from the\u003cbr /\u003e isomeric mixture was accomplished by repeated recrystallizations from the solution\u003cbr /\u003e in a CH\u003csmall\u003e2\u003c/small\u003eCl\u003csmall\u003e2\u003c/small\u003e-MeOH mixed solvent.  As a result, the isomeric mixture of 44.8 mg afforded\u003cbr /\u003e 22.5 mg of the target 1-Zn to be pure at NMR level.  The characterization of the\u003cbr /\u003e target porphyrin has been carried out by \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectroscopies and HR\u003cbr /\u003e FAB-MS spectrometry.  The central zinc atom was demetallated under the acidic\u003cbr /\u003e condition with TFA in CH\u003csmall\u003e2\u003c/small\u003eC\u003csmall\u003el2\u003c/small\u003e and the freebase porphyrin 1-H\u003csmall\u003e2\u003c/small\u003e was obtained in 98%\u003cbr /\u003e yield.  The insertion of copper ions was carried out by refluxing the solution of 1-H\u003csmall\u003e2\u003c/small\u003e\u003cbr /\u003ein the presence of Cu(OAc)\u003csmall\u003e2\u003c/small\u003e・H\u003csmall\u003e2\u003c/small\u003eO, which resulted in target compound 1-Cu\u003cbr /\u003e quantitatively.\u003cbr /\u003e　The supramolecular integration of the obtained porphyrins 1-H\u003csmall\u003e2\u003c/small\u003e and 1-Cu has been\u003cbr /\u003e examined in some polar solvents by taking advantageous of the amphiphilic properties\u003cbr /\u003e of the porphyrins.  The UV-Vis spectral changes were observed on adding H\u003csmall\u003e2\u003c/small\u003eO to the\u003cbr /\u003e solution of the freebase 1-H\u003csmall\u003e2\u003c/small\u003e in THF.  The Soret absorption band of 1-H\u003csmall\u003e2\u003c/small\u003e shows red shift\u003cbr /\u003e by 42 nm.  Similar behaviors were observed for the absorption experiments of 1-H\u003csmall\u003e2\u003c/small\u003e\u003cbr /\u003e upon cooling the hot MeOH solution.  On the other hand, when H\u003csmall\u003e2\u003c/small\u003eO was added to the\u003cbr /\u003e solution of 1-Cu in THF, the Soret band of 1-Cu at 397 nm displayed clear blue shifts\u003cbr /\u003e with a peak (\u003ci\u003e\u0026lambda;\u003c/i\u003e\u003csmall\u003emax\u003c/small\u003e) at 392 nm in THF : H\u003csmall\u003e2\u003c/small\u003eO = 1 : 9 mixed solvent.  In general, Kasha’\u003cbr /\u003es exciton theory predicts that a blue shift observed in the optical absorption indicates a\u003cbr /\u003e face-to-face H-aggregation of the chromophores.\u003cbr /\u003e　The shapes of the nanostructures of the integrated porphyrin assemblies have been\u003cbr /\u003e confirmed by the SEM and TEM observations.  When the suspension of freebase\u003cbr /\u003e porphyrin 1-H\u003csmall\u003e2\u003c/small\u003e precipitated from the hot MeOH solution was casted on a substrate, the\u003cbr /\u003e TEM image revealed a rod structure that consists of the bundles of wires with the\u003cbr /\u003e diameter of about 25 nm.  The precipitate of 1-Cu obtained from THF-H\u003csmall\u003e2\u003c/small\u003eO showed short\u003cbr /\u003e rod-like structures with the diameter of around 11 nm and the length in the range of\u003cbr /\u003e 140－310 nm as estimated from the SEM and TEM observations.  The SEM image of\u003cbr /\u003e the precipitate of 1-Cu obtained from a hot MeOH solution afforded a helical\u003cbr /\u003e ribbon-structure without chiral selectivity.\u003cbr /\u003e　The XRD analysis of the precipitate of 1-Cu from THF-H\u003csmall\u003e2\u003c/small\u003eO solution revealed that\u003cbr /\u003e the molecules are packed in a monoclinic unit cell with the dimensions of \u003ci\u003ea\u003c/i\u003e = 67.71(4), \u003ci\u003eb\u003c/i\u003e\u003cbr /\u003e = 3.546(3) and c = 24.62(2)  Åand β = 96.72(7)° and the π-stacked 1-D chains are aligned to the \u003ci\u003eb\u003c/i\u003e-axis with the π-stacking distance of 3.55 Å.\u003cbr /\u003e　I investigated the thermal magnetic behaviors of 1-Cu with SQUID measurements\u003cbr /\u003e in order to confirm the intermolecular metal-metal interaction induced by the\u003cbr /\u003e supramolecular integration.  The magnetic susceptibility of the precipitate obtained\u003cbr /\u003e from THF-H\u003csmall\u003e2\u003c/small\u003eO solution shows a bent on decreasing temperature, which indicates a weak magnetic interaction between the Cu(II) centers.  The Curie-Weiss plot of the\u003cbr /\u003e susceptibility between 4-300 K affords the Weiss constant as -0.22 K.  The induction of\u003cbr /\u003e intermolecular magnetic interaction between metal centers with soft-material systems is\u003cbr /\u003e rare.\u003cbr /\u003e　The supramolecular integration of the porphyrin without any solvents has been also\u003cbr /\u003e investigated by slow cooling from the melting state.  The DSC measurement and the\u003cbr /\u003e POM observation of 1-Cu showed that the melting point was \u003ci\u003eca\u003c/i\u003e. 130 ℃ and the\u003cbr /\u003e porphyrin was thermally stable upto this temperature region.  When 1-Cu was heated\u003cbr /\u003e over 130 ℃, fluid-like porphyrin was observed.  After cooling to r. t., integrated 1-Cu\u003cbr /\u003e was obtained easily and the UV-Vis spectrum and the XRD analysis of this aggregate\u003cbr /\u003e suggested a similar supramolecular structure as 1-Cu precipitates obtained from the\u003cbr /\u003e solution in polar solvents.\u003cbr /\u003e　In summary, I have succeeded in the syntheses of novel amphiphilic porphyrin\u003cbr /\u003ecomplexes, investigated their self-assembly behaviors and the properties of the\u003cbr /\u003eassembled nanostructures.", "subitem_description_type": "Other"}]}, "item_1_description_18": {"attribute_name": "フォーマット", "attribute_value_mlt": [{"subitem_description": "application/pdf", "subitem_description_type": "Other"}]}, "item_1_description_7": {"attribute_name": "学位記番号", "attribute_value_mlt": [{"subitem_description": "総研大甲第1313号", "subitem_description_type": "Other"}]}, "item_1_select_14": {"attribute_name": "所蔵", "attribute_value_mlt": [{"subitem_select_item": "有"}]}, "item_1_select_16": {"attribute_name": "複写", "attribute_value_mlt": [{"subitem_select_item": "全文複写可"}]}, "item_1_select_17": {"attribute_name": "公開状況", "attribute_value_mlt": [{"subitem_select_item": "全文公開可"}]}, "item_1_select_8": {"attribute_name": "研究科", "attribute_value_mlt": [{"subitem_select_item": "物理科学研究科"}]}, "item_1_select_9": {"attribute_name": "専攻", "attribute_value_mlt": [{"subitem_select_item": "07 構造分子科学専攻"}]}, "item_1_text_10": {"attribute_name": "学位授与年度", "attribute_value_mlt": [{"subitem_text_value": "2009"}]}, "item_creator": {"attribute_name": "著者", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "ODA, Masafumi", "creatorNameLang": "en"}], "nameIdentifiers": [{"nameIdentifier": "0", "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": "2016-02-17"}], "displaytype": "simple", "download_preview_message": "", "file_order": 0, "filename": "甲1313_要旨.pdf", "filesize": [{"value": "342.6 kB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_11", "mimetype": "application/pdf", "size": 342600.0, "url": {"label": "要旨・審査要旨", "url": "https://ir.soken.ac.jp/record/1651/files/甲1313_要旨.pdf"}, "version_id": "31b88a0d-8328-4aec-9a59-422648c0f91a"}, {"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2016-02-17"}], "displaytype": "simple", "download_preview_message": "", "file_order": 1, "filename": "甲1313_本文.pdf", "filesize": [{"value": "37.2 MB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_11", "mimetype": "application/pdf", "size": 37200000.0, "url": {"label": "本文", "url": "https://ir.soken.ac.jp/record/1651/files/甲1313_本文.pdf"}, "version_id": "a2cf70eb-ab64-4439-9d6b-b777ec2baa0f"}]}, "item_language": {"attribute_name": "言語", "attribute_value_mlt": [{"subitem_language": "eng"}]}, "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": "Synthesis and Supramolecular Assembly of Highly Planar Amphiphilic Porphyrin Complexes", "item_titles": {"attribute_name": "タイトル", "attribute_value_mlt": [{"subitem_title": "Synthesis and Supramolecular Assembly of Highly Planar Amphiphilic Porphyrin Complexes"}, {"subitem_title": "Synthesis and Supramolecular Assembly of Highly Planar Amphiphilic Porphyrin Complexes", "subitem_title_language": "en"}]}, "item_type_id": "1", "owner": "21", "path": ["9"], "permalink_uri": "https://ir.soken.ac.jp/records/1651", "pubdate": {"attribute_name": "公開日", "attribute_value": "2011-01-14"}, "publish_date": "2011-01-14", "publish_status": "0", "recid": "1651", "relation": {}, "relation_version_is_last": true, "title": ["Synthesis and Supramolecular Assembly of Highly Planar Amphiphilic Porphyrin Complexes"], "weko_shared_id": -1}