Synthesis and Physical Properties of Novel Cationic Disk-shaped Molecules
| Project/Area Number |
17550041
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Tokyo Metropolitan University |
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Principal Investigator |
SATO Kiyoshi Tokyo Metropolitan University, Graduate School of Urban Enviromenttal Sciences, Research Associate, 都市環境科学研究科, 助教 (40285101)
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| Project Period (FY) |
2005 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 2006: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2005: ¥1,200,000 (Direct Cost: ¥1,200,000)
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| Keywords | Azoniacoronene / Polycyclic Aromatics / Azonia Aromatic Compounds / Heterocoronene / Heterohelicene / Intramolecular Diels-Alder Reaction / Photocyclization |
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| Research Abstract |
The disk-shaped polycyclic aromatic hydrocarbon, "coronene", is a one of the most fascinating molecules, and whose structural feature shows promising application for organic photo-electron materials and devices such as columnar liquid crystals, organic transistors, electro-luminescence displays, and organic solar cells. Replacement of the benzene ring of coronene by a heterocycle would be expected to change their electronic and structural properties. Some heterocoronenes (or heterocirculenes), including thiophene, furan, or pyridazine rings have been reported until now. However, azonia derivative of coronene, in which a bridehead carbon atom replaced by quaternary nitrogen atom, was still unknown.
In this study, we have discovered an efficient synthesis of azoniacoronene by novel photo-induced intra-molecular Diels-Alder type reaction of azoniathia[6]helicenes. Irradiation to an acetonitrile solution of, 9-(2-naphthylvinyl)-thieno- quinolizinium salt gave the azoniacoronene in 80% yield
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by the intra-molecular photo-Diels-Alder type reaction followed by the oxidative-photocyclization. Photoreaction of 2-(3-thiophenyl)-naphto[1,2-a]quinolizinium also gave azoniacoronene in 82% yield. Applying this new reaction, we tried to obtain 2a,8a-diazoniacoronene having two quaternary nitrogen atoms. Stepwised condensation of 2,8-dimethylquinolizinium with 3-thiophenaldehyde and pyridine-4-carboaldehyde afforded an unsymmetric diolefin. Photoreaction of the diolefin gave 2a,8a-diazoniacoronene in 5% yield with a pyridone type by-product. Diazonia derivative of doublecoronene was also obtained by this reaction.
The azoniacoronene shows a strong luminescence in dilute solution. However, increase of solvent concentration or polarity, the fluorescence spectrum shifts to longer wavelength with decrease of the quantum yield due to self-aggregation confirmed by UV/vis, fluorescent, and NMR titration studies. We also found the fluorescent property of azoniacoronene-polyanion complexes, such as polyion-complex with anionic polymer or intercalated layered inorganic material, are depending on the polyanionic matrices, and the cation exchange ratio of the polyion complexes also affects the optical properties. Less
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Report
(3 results)
Research Products
(2 results)
