{"created":"2023-06-20T13:21:18.781529+00:00","id":1465,"links":{},"metadata":{"_buckets":{"deposit":"5d14992e-9155-4c8e-b990-9a7d621a7978"},"_deposit":{"created_by":21,"id":"1465","owners":[21],"pid":{"revision_id":0,"type":"depid","value":"1465"},"status":"published"},"_oai":{"id":"oai:ir.soken.ac.jp:00001465","sets":["2:427:9"]},"author_link":["0","0","0"],"item_1_creator_2":{"attribute_name":"著者名","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"三宅, 雄介"}],"nameIdentifiers":[{}]}]},"item_1_creator_3":{"attribute_name":"フリガナ","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"ミヤケ, ユウスケ"}],"nameIdentifiers":[{}]}]},"item_1_date_granted_11":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"2009-03-24"}]},"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_12":{"attribute_name":"要旨","attribute_value_mlt":[{"subitem_description":"1. Introduction<br />　　　Construction of well ordered surface structures with functional molecular<br />building blocks have attracted much attentions because of their potential applications<br />for novel functional materials. In recent years, surface modification using<br />self-assembly of organic molecules has been significantly advanced by scanning<br />tunneling microscopy (STM) in ultra-high-vacuum (UHV)<sup>1,2</sup> or under ambient<br />conditions.<sup>3,4,5,6,7,8</sup>Especially, in situ</i> STM at the solid-liquid interfaces<sup>3</sup> is a powerful<br />and useful technique to characterize local surface structure, electronic state and<br />surface dynamics of materials composed by organic molecules with submolecular<br />resolution. Numbers of self-assembled structures on surfaces have been observed using <i>in situ</i> STM at the solid-liquid interface. <sup>3,4,5, 6,7,8</sup>  However, few report focused on<br />influence of intermolecular and/or moleculai-surface interactions of the component<br />molecules systematically for the stable structures formed at the solid-liquid interface. <br />I have investigated systematically the effects of the molecular structure on<br />self-organized structure of porphyrin and naphthalenediimide, and their surface<br />dynamics to explore new surface modification method based on self-assembled<br />structures<br /><br />2. Investigation of Vanadyl and Cobalt(II) Octaethylporphyrin Self-Assembled<br />Monolayer Arrays on Highly Oriented Pyrolytic Graphite (HOPG) by STM<br />　　　Porphyrin and related compounds not only play an important role in<br />photosynthesis, biochemistry and catalysis in nature, but are also important<br />candidates for building blocks of future molecular devices.<sup>9</sup> These compounds also have attracted significant attentions in the fields of life science, material science and<br />physics because of their unique electronic structures, spectroscopic properties based<br />on the large conjugated π-electron system and existence of metal coordination sites. <br />Fundamental characterization of porphyrin metallate self-assembled structures by<br />STM will contribute significantly to future applications of molecular devices. <br />Two-dimensional crystals of ［2,3,7,8,12,13,17,18-octaethyl 21<i>H</i>,23<i>H</i>-porphine］<br />vanadium（IV)oxide and cobalt(II) (VOOEP and CoOEP, respectively) at the interface of<br />1-tetradecene and HOPG surface were studied by STM. The lattice parameters were<br />determined for VOOEP (<i>a</i> = 1.61&plusmn;0.1 nm, <i>b</i>= 1.46&plusmn;0.05 nm, <i>&Gamma;</i>=61&plusmn;3<small>○</small>) and CoOEP<br />(<i>a</i> = 1.48&plusmn;0.08 nm, <i>b</i>= 1.42&plusmn;0.07nm, <i>&Gamma;</i>=62.0&plusmn;4<small>○</small>), which were calibrated using the<br />HOPG lattice as the reference. High-resolution STM showed different type of the<br />images for these two porphyrin molecules. The STM image of VOOEP was a square<br />shape with four fold bright spots probably corresponding to the π-system of the<br />porphyrin ring, and that of CoOEP showed a bright spot at the center metal site. <br />3. Effect of Alkyl Chain Length to the Two-Dimensional Structure and STS Studies of<br />N, N'-bis(alkyl)naphthalenediimide on HOPG<br />　　　Long alkyl chains are widely utilized as \"anchor\" groups for immobilizing<br />organic molecules on graphite surface under ambient conditions in STM measurements. <br />However, few report focused on effects of the alkyl chain length to self-assembled<br />structures on HOPG systematically.　STM investigations of self assembled structures<br />of N,N'-bis(alkyl)naphthalenediimide (NDI) with a series alkyl chains ranging from<br />propyl to octadecyl were carried out at l-tetradecene/HOPG interface. NDI derivatives<br />were prepared by the usual condensation reactions. Each NDI derivatives is<br />abbreviated as CX-NDI (X is the corresponding carbon number of alkyl chains). The<br />self'-assembled structure of them on HOPG showed strong dependence on the alkyl<br />chain length. I classified them into six types; (1) linear arrays with row lattice<br />structure was observed in C3-NDI and C4-NDI, (2) chiral windmill structure in C4 and<br />C5-NDI, (3) honeycomb structure in C6〜C9-NDI, (4) chiral honeycomb structure in C10<br />and C12-NDI, (5) pseudo honeycomb structure containing super lattice in C11-NDI, (6) <br />typical alkyl lamellar structure in C13〜C18-NDI. In the self-assembled structure of C4, <br />C5, C10, C11 and C12-NDI, meta-stable state structures were also observed. Molecular<br />dynamics (MD) simulation for C3, C4, C9 and C18 are well coincident with the STM<br />observations. Results of STM, MD simulation and X-ray single crystallography of<br />C4-NDI clearly suggest that CH/O hydrogen bonding interaction is the critical driving<br />force for the self-assembling. <br /><br />4. Surface Dynamics and Nano-Size-Manipulation on Self-Assembled N,N'-bis(alkyl)<br />naphthalenediimide on Graphite<br />　　　During the STM observation of the self-assembled structure of NDI, thermally<br />meta-stable states were found. I investigated dependence of the self-assembled<br />structure of C11-NDI on temperature. A distort honeycomb structure was observed as a<br />meta-stable state of C11-NDI, which converted to the thermally stable structure<br />containing super lattice upon heating.　The dynamic transition of' the former<br />structure to the latter was also observed. <br /><br />5. Conclusion<br />　I have investigated self-assembled structures of porphyrin and NDI derivatives in<br />order to explore new self-assembled method and phenomena of surface dynamics. <br />　Self-assembled structures of two metallo octaethylporphyrins, VOOEP and CoOEP, <br />were structurally characterized using STM. High-resolution STM images reflecting<br />difference of the central metal were obtained. <br />　Self assembled structures of NDI with a series of alkyl chain length ranging from<br />propyl to octadecyl (excluding heptadecyl) were characterized using STM at<br />1-tetradecene / HOPG interface. Structural transition induced by the difference of<br />alkyl chain length was observed on self-assembled 2D structures of NDI derivatives. <br />Competition of inter-molecular CH/O type hydrogen bonding interaction and intermolecular alkyl-alkyl interaction lead to complex self-assembled structures on<br />HOPG. Thermal effects to the self-assembled structures were also investigated. <br />Direct observation of a local structural transition was succeeded on C11-NDI<br />self-assembled structure. <br />　These surface studies described above will open a new method for self-assembled and solution-processed nano-fabrication.","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1221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":"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":"2008"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"MIYAKE, Yusuke","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1221_要旨.pdf","filesize":[{"value":"308.7 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"要旨・審査要旨","url":"https://ir.soken.ac.jp/record/1465/files/甲1221_要旨.pdf"},"version_id":"34befe5c-45bd-4ad4-a1de-f56dc4f8b282"}]},"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":"Analysis of Versatile Self-assembled Two Dimensional Structures of N, N'-bis (alkyl) Naphthalene-diimide on Graphite Using Scanning Tunneling Microscopy and Computer Simulation","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Analysis of Versatile Self-assembled Two Dimensional Structures of N, N'-bis (alkyl) Naphthalene-diimide on Graphite Using Scanning Tunneling Microscopy and Computer Simulation"},{"subitem_title":"Analysis of Versatile Self-assembled Two Dimensional Structures of N, N'-bis (alkyl) Naphthalene-diimide on Graphite Using Scanning Tunneling Microscopy and Computer Simulation","subitem_title_language":"en"}]},"item_type_id":"1","owner":"21","path":["9"],"pubdate":{"attribute_name":"公開日","attribute_value":"2010-03-25"},"publish_date":"2010-03-25","publish_status":"0","recid":"1465","relation_version_is_last":true,"title":["Analysis of Versatile Self-assembled Two Dimensional Structures of N, N'-bis (alkyl) Naphthalene-diimide on Graphite Using Scanning Tunneling Microscopy and Computer Simulation"],"weko_creator_id":"21","weko_shared_id":-1},"updated":"2023-06-20T16:03:34.932036+00:00"}