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縮合１，２，５ - チアジアゾール環を有する新規有機酸化還元系の研究
https://ir.soken.ac.jp/records/153
https://ir.soken.ac.jp/records/15318cf746d-9bf6-49df-ad27-f753459c7af1
| 名前 / ファイル | ライセンス | アクション |
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要旨・審査要旨 / Abstract, Screening Result (324.2 kB)
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本文 (2.2 MB)
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| Item type | 学位論文 / Thesis or Dissertation(1) | |||||
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| 公開日 | 2010-02-22 | |||||
| タイトル | ||||||
| タイトル | 縮合１，２，５ - チアジアゾール環を有する新規有機酸化還元系の研究 | |||||
| タイトル | ||||||
| タイトル | Studies on Novel Organic Redox SystemsContaining Fused 1,2,5-Thiadiazole Rings | |||||
| 言語 | en | |||||
| 言語 | ||||||
| 言語 | eng | |||||
| 資源タイプ | ||||||
| 資源タイプ識別子 | http://purl.org/coar/resource_type/c_46ec | |||||
| 資源タイプ | thesis | |||||
| 著者名 |
小野, 克彦
× 小野, 克彦 |
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| フリガナ |
オノ, カツヒコ
× オノ, カツヒコ |
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| 著者 |
ONO, Katsuhiko
× ONO, Katsuhiko |
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| 学位授与機関 | ||||||
| 学位授与機関名 | 総合研究大学院大学 | |||||
| 学位名 | ||||||
| 学位名 | 博士（理学） | |||||
| 学位記番号 | ||||||
| 内容記述タイプ | Other | |||||
| 内容記述 | 総研大甲第121号 | |||||
| 研究科 | ||||||
| 値 | 数物科学研究科 | |||||
| 専攻 | ||||||
| 値 | 07 構造分子科学専攻 | |||||
| 学位授与年月日 | ||||||
| 学位授与年月日 | 1995-03-23 | |||||
| 学位授与年度 | ||||||
| 値 | 1994 | |||||
| 要旨 | ||||||
| 内容記述タイプ | Other | |||||
| 内容記述 | Recently much attention has been focused on development of organic conductors and superconductors. For this purpose, syntheses of new electron donors and acceptors are very important. One of the important points for the molecular design is to extend π-conjugation in order to reduce on-site Coulombic repulsion. The other is to form highly dimensional crystal structures. From these viewpoints, 1,2,5-thiadiazole rings are of interest since they have extended π-conjugation and polarized heteroatoms resulting in strong intermolecular interactions by heteroatom contacts. Furthermore, since thiadiazoles are electron-withdrawing heterocycles, compounds with both thiadiazole rings and electron-donating ones are expected to have a high polarizability, intramolecular chargetransfer (CT) interaction, and an enhanced amphoteric redox ability. In this research work, He designed some new types of redox systems containing thiadiazole moieties and investigated their electronic properties and crystal structures. Chapter 1 describes the purpose and some attractive previous works as introduction of this thesis. Chapter 2 describes preparation, properties, and an X-ray crystal structure analysis of 7- (1, 3-dithiol-2-ylidene)-4-methyl-4, 7-dihydro[1, 2, 5]thiadiazolo[3, 4-b]pyridine. The compound and its derivatives were characterized by intramolecular CT bands around 510 and 490 nm and stronger electron-donating abilities than tetrathiafulvalene (TTF) in the cyclic voltammetry (CV) study, indicating that they are of interest as novel electron donors which have no TTF skeleton. The crystal analysis revealed that the molecules make columnar stacks and the overlapping is in accord with an effective interaction between the HOMO and the LUMO. The crystal structure is composed of a set of four columns interacted with each other through short S･･･S contacts. Although the net atomic charges calculated by the MNDO-PM3 method show that the molecule is highly polarized, S･･･N contacts arising from an electrostatic effect were not observed. The compounds formed conducting CT complexes with tetracyanoquinodimethane. One of them showed a high electrical conductivity (1 S cm-1) as a compressed pellet, and the degree of CT was evaluated as 0.67 according to the C=N stretching frequency. The cation radical salts were prepared by an electrochemical oxidation, and the C104 salt of the ethylenedithio-derivative showed a semiconducting behavior with a σrt=4. 4x10-2Scm- tandEa=0. 15eV Nonplanar donors or acceptors giving organic conductors are very few. Chapter 3 describes a novel nonplanar donor molecule containing fused benzene and fused thiadiazloe rings. The unique butterfly-shaped structure and intramolecular short S･･･N contacts were revealed by an X-ray crystal structure analysis, and a uniform columnar stacking was also observed. Although many organic conductors are known, they are composed of multi-components such as CT complexes. Usual organic compounds are insulators as single components. However, molecules containing both donor and acceptor units are expected to exhibit unusual electrical properties owing to intramolecular CT interaction. 4H, 8H4-,8-Bis (1, 3-dithiol-2-ylidene) benzo [1, 2-c : 4, 5c']bis[1,2,5]thiadiazole(BTQBT) is one of the most electrical conducting materials as a single component. Its electrical behavior is ascribable to strong intermolecular interactions in the crystal. He have now replaced one of the 1, 3-dithiole groups by a carbonyl group to give BTQT, which is considerable to be more polarized than BTQBT. Chapter 4 deals with an X-ray crystal structure analysis and an electrical behavior of BTQT. In the crystal the molecular over lapping is close to that of BTQBT, suggesting intermolecular CT interaction. The overlap mode is caused from the most effective interaction between the HOMO and the LUMO. On the other hand, the crystal structure is in sharp contrast with that of BTQBT, which makes a sheet-like network with short S･･･S contacts. BTQT molecules are three-dimensionally connected with each other through short S･･･S, S･･･N, and S･･･O contacts. These S･･･N and S･･･O contacts are attributed to an electrostatic effect due to the highly polarized structure. The electrical conducting behavior fails to obey Ohm's law. The current increased approximately in proportion to the third power of the voltage. The non-ohmic behavior observed here is an unprecedented one as organic crystals. Chapter 5 is concerned with novel heterocycles, benzo[1, 2-c:4,5-c' ]bis ([1, 2, 5]thiadiazole)s and the monoselenium analogues, which contain a tetravalent sulfur atom. They are characterized by higher electron affinities and longer absorption maxima compared with those of a related Kekule-type isomer. The high electron affinities are owing to the unique 14π-electron ring system containing a tetravalent sulfur atom, which generates a more stable Kekule-type thiadiazole ring upon accepting an electron. Their electron-accepting abilities are comparable to that of p-benzoquinone. They showed strong fluorescence emission. Their electronic properties and reactivities are explained by the MNDO-PM 3 calculations. In the X-ray crystal structure analysis of the dibromoderivative, the molecular structure demonstrates the hypervalency on the sulfur atoms and the 14π-electron ring moiety. The crystal structure is composed of a set of two ribbon columns linked by short S･･･N and N･･･N contacts, and these columns interact with each other through short Br･･･N contacts resulted in a dense crystal packing. The donor-π-acceptor molecules were also synthesized by introduction of electron-donating groups into the skeleton. Their redox potentials were determined by the CV study. The molecules substituted by arnine groups show good amphoteric redox properties. The electron-donating ability of the dimethylaminobenzene derivative is similar to that of TTF, indicating that it is a promising electron donor for organic conductors. At the end of the thesis, this research work is summarized and makes some suggestions. Introduction of 1,2,5-thiadiazole rings into electron donors results in large polarization, which is helpful to stabilize the ring systems. Highly polarized molecules show interesting physical properties. Unique molecular assemblies are constructed by intermolecular interactions between polarized heteroatoms. Control of physical properties and crystal structures of such molecules seems possible by changing the polarizability affected by the charge densities on the heteroatoms. |
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| 値 | 有 | |||||
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| 内容記述タイプ | Other | |||||
| 内容記述 | application/pdf | |||||
