{"created":"2023-06-20T13:20:09.157658+00:00","id":159,"links":{},"metadata":{"_buckets":{"deposit":"106a866f-3019-4e74-b791-6569489b32f2"},"_deposit":{"created_by":1,"id":"159","owners":[1],"pid":{"revision_id":0,"type":"depid","value":"159"},"status":"published"},"_oai":{"id":"oai:ir.soken.ac.jp:00000159","sets":["2:427:9"]},"author_link":["7674","7676","7675"],"item_1_creator_2":{"attribute_name":"著者名","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"太田, 哲"}],"nameIdentifiers":[{}]}]},"item_1_creator_3":{"attribute_name":"フリガナ","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"オオタ, アキラ"}],"nameIdentifiers":[{}]}]},"item_1_date_granted_11":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"1996-03-21"}]},"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_12":{"attribute_name":"要旨","attribute_value_mlt":[{"subitem_description":"  In the field of materials chemistry, the 1, 3-dithiole ring system is one of the most widely investimated and attractive heterocvcles due to its unique redox properties.  A large number of new orazanic materials containing this svstem have been developed.  The most important examale is tetra-thiafulvalene (TTF) and related electron donors giving organic conductors or superconductors.  2-Methylene-1, 3-dithiole, which is a component of TTF, is considered to give the corresponding cation radical upon one-electron oxidation.  In other words, it can be regarded as a source of cation radical species.  Thus, introduction of this unit into an appropriate π-electron system is expected to produce various novel redox systems showing interesting properties and reactivities inherent to the configuration and the number of the 1, 3-dithiole units as well as to the nature of the π-electron system.  Therefore, on the development of novel organic functional materials as well as organic conductors, it is worthwhile to prepare such redox systems and study theirproperties.\n  In this thesis, the author designed several novel 1, 3-dithiole compounds containing thiophene-related systems and investigated their electrochemical properties, reactivities, and crystal structures.  The thiophene derivatives were chosen as spacer units for following reasons. (i) The electron-releasing thiophene ring is expected to enhance the electron-donating ability of the molecules and to stabilize the cationic species formed by oxidation.  (ii) The expansion of π-conjugation caused by insertion of the thiophene units may reduce intramolecular Coulombic repulsion.  (iii) The structural modification is generally easy.\n  The present thesis consists of the following four chapters.  Chapter 1 describes the recent studies related to this research work and the purpose and constitution of the thesis.\n  In Chapter 2, 6, 6-bis[5-(1, 4-dithiafulven-6-yl)-2-thienyl]-1, 4-dithiafulvene and its derivatives have been prepared as novel cross-conjugated tris(1, 3-dithiole) donors, and their physical and chemical properties are discussed.  According to MNDO-PM3 calculations on a parent compound, the molecule takes a nonplanar conformaation, in which one dithiafulvenyl unit is orthogonal to the plane of the 2, 5-bis(dithiafulvenyl)thiophene skeleton.  The cyclic voltammograms (CV) showed that the donors are oxidized to trication radicals or tetracations.  The first oxidation waves correspond to two-electron processes, indicating the reduced on-site Coulombic repulsion in the dication State.  The electron-donating ability of the donors is estimated to be comparable to that of TTF.  The donors gave iodine complexes which showed electrical conductivities of 10-5  - 10-2 Scm-1 as comtressed pellets.  A redox active polymer was formed from a certain derivative by electrochemical oxidation.  Furthermore, the synthesis and redox aroaerties of a tris(1, 3-dithiole) donor containing a cyclopentadithiophene moiety were also discussed.\n  Chapter 3 deals with the preparation and properties of bis(1, 3-dithiole) compounds containins thienylmethylene units affording novel cations by oxidation.  Molecules possessing a methylene group adjacent to electron-donating moieties seem to undergo deprotonation by oxidation to give the corresponding methyl cations.  In order to prove the generality of this type of reaction and to apply it to the preparation of novel cations, bis(1, 3-dithiole) compounds containing a dithienylmethane skeleton have been prepared.  The CV indicated that redox active products were formed through electrochemical oxidation followed by chemical reactions and the reactions were dependent on the substituents R on the C6-carbons of the dithiafulvenyl groups.  When R was methyl group, chemical oxidation of the compounds with NOBF4 gave the corresponding dithienylmethyl cations in moderate yields.  They were also obtained by hydride abstraction with Ph3CBF4.  The cations were characterized by intense absorptions in the near-infrared region (900-980nm in MeCN).  The alkylthio groups on the dithiole rings make the absorptions much red-shifted.  The absorption band was blue-shifted to ca. 820 nm in a thin film, indicating that they are interesting as near-infrared absorbing dyes.  The polymethine cyanine like structure of the cation was revealed by the X-ray analysis.  On the other hand, in the case of R=H, a redox active oligomer was formed by oxidation.  Furthermore, isolation of the dication salt derived from 2, 5-bis[5-(6-methyl-1, 4-dithiafulven-6-yl)-2-thienylmethyl]thiophene, which has two methylene groups, was also attempted.\n  Although it has been reported that 1, 4-dithiafulvene derivatives undergo oxidative intermolecular coupling reactions at the 6-position, the corresponding intramolecular reaction is unknown. Chapter 4 describes the oxidative intramolecular cvclization of 2, 2'-bis(1, 4-dithiafulven-6-yl)-3, 3'-bithienyls.  The CVs of the compounds showed that they are irreversibly oxidized to afford redox active aroducts.  Chemical oxidation with tris(4-bromophenyl) aminium hexachloroantimonate gave cyclization products as dication salts in high yields.  The X-ray structural analyses of the dication salts revealed that they contain trivalent chloroantimonate ions (Sb2Cl8 2- and SbCl5 2-), suggesting that SbCl6- ion acts as an oxidizing agent in the reaction.  Chemical reduction of the dication salts with zinc gave the corresponding neutral donors in high yields.  According to the X-ray analysis, the molecule adopts a nonplanar structure,with short intramolecular S…S contacts.  The CVs of the donors showed reversible one-stage two-electron oxidation waves, and the potentials are fairly low compared with TTF.  A tetracyano-quinodimethane complex was formed from one of them.","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179号","subitem_description_type":"Other"}]},"item_1_select_14":{"attribute_name":"所蔵","attribute_value_mlt":[{"subitem_select_item":"有"}]},"item_1_select_8":{"attribute_name":"研究科","attribute_value_mlt":[{"subitem_select_item":"数物科学研究科"}]},"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":"1995"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"OHTA, Akira","creatorNameLang":"en"}],"nameIdentifiers":[{}]}]},"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","filename":"甲179_要旨.pdf","filesize":[{"value":"309.6 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"要旨・審査要旨 / Abstract, Screening Result","url":"https://ir.soken.ac.jp/record/159/files/甲179_要旨.pdf"},"version_id":"8c010162-b41b-4261-96c8-4b0a9fbe1205"},{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2016-02-17"}],"displaytype":"simple","filename":"甲179_本文.pdf","filesize":[{"value":"12.4 MB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"本文","url":"https://ir.soken.ac.jp/record/159/files/甲179_本文.pdf"},"version_id":"ecba3e82-0e38-4a81-8011-36f7682e6c8d"}]},"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":"Studiesis of Novel 1,3-Dithiole Compounds Containing Thiophene-Related Systems","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Studiesis of Novel 1,3-Dithiole Compounds Containing Thiophene-Related Systems"},{"subitem_title":"Studiesis of Novel 1,3-Dithiole Compounds Containing Thiophene-Related Systems","subitem_title_language":"en"}]},"item_type_id":"1","owner":"1","path":["9"],"pubdate":{"attribute_name":"公開日","attribute_value":"2010-02-22"},"publish_date":"2010-02-22","publish_status":"0","recid":"159","relation_version_is_last":true,"title":["Studiesis of Novel 1,3-Dithiole Compounds Containing Thiophene-Related Systems"],"weko_creator_id":"1","weko_shared_id":1},"updated":"2023-06-20T15:00:06.164311+00:00"}