2019 Fiscal Year Research-status Report
Iron-catalyzed Activation of Unreactive Bonds for Organic Materials Synthesis
| Project/Area Number |
19K15555
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| Research Institution | The University of Tokyo |
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Principal Investigator |
シャン ルイ 東京大学, 大学院理学系研究科(理学部), 特任講師 (50793212)
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| Project Period (FY) |
2019-04-01 – 2022-03-31
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| Keywords | spiro-conjugated / C-H alkynylation / iron-catalyzed / C-H activation / cyclization / phenylenevinylene |
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| Outline of Annual Research Achievements |
A series of novel spiro-conjugated carbon-bridged phenylenevinlene materials was developed using C-H activation as key synthetic steps. Materials properties and post-synthetic derivatization of these materials were investigated. These spiro-molecules are chiral and optical resolution was successfully achieved through derivatization. The spiro-conjugated chiral molecules exhibit circularly polarized photoluminescence with very high photoluminescence quantum yield and chemical stability. These spiro-conjugated materials are currently under investigation as new hole transporting materials and light emitting materials in devices. These results were published already in JACS this year.
A C-H activation/alkynylation method was developed using low cost chromium-catalysis without exogenous ligand for synthesis of diarylalkynes, which are critical intermediates for synthesis of conjugated materials. These results revealed historically overlooked reactivity of chromium(III) species and open new horizon in developing chromium catalysis for C-H activation. This achievement was already published in JACS early this year.
We currently achieved and are developing iron-catalyzed methods through C-H activation and C-O activation to access semiconductive organic polymers of thiophenes, and carbon-bridged phenylene-vinylene-thienylene materials. These materials will be tested as new charge transporting materials and near infrared absorption materials.
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| Current Status of Research Progress |
Current Status of Research Progress
1: Research has progressed more than it was originally planned.
Reason
As we planned, we achieved iron-catalyzed thienyl C-H/C-H coupling without using directing groups to regioselectively couple thiophene derivatives. This method is useful to synthesize small molecular, oligomeric, and polymeric thiophene based organic semiconductors as optoelectronic or charge transfer materials. Also, we successfully achieved iron-catalyzed method to synthesize conjugated carbon-bridged phenylenevinylene derivatives in short synthetic steps. The iron-catalysis method enables further synthesis of unprecedented carbon-bridged arylenevinylene with tolerance of functional groups incompatible in previous synthesis. To develop near IR absorption materials using these conjugated materials is on going. We expect these results will be wrapped into two publications this fiscal year.
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| Strategy for Future Research Activity |
With the iron-catalyzed synthetic method developed and optimized, and our experience in developing conjugated materials such as spiro-conjugated phenylenevinylenes during last fiscal year, we will focus on synthesis of thiophene based organic small molecular and polymeric materials with concurrent investigation of their functions. Iron-catalyzed C-H/C-H polymerization to construct semiconductive materials for device application presents one of the holy grails in synthetic chemistry. Novel types of polymers with high molecular weight will be made. Their properties and functions in optoelectronic devices will be investigated. At the same time, we will use iron-catalyzed C-O activation/cyclization method to construct unprecedented carbon-bridged arylenecinylenes with the aim to develop NIR materials.
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[Journal Article] Spiro-conjugated Carbon/Heteroatom-bridged p-Phenylenevinylenes: Synthesis, Properties, and Microcrystal Electron Crystallographic Analysis of Racemic Solid Solutions2020
Author(s)
H. Hamada, T. Nakamuro, K. Yamashita, H. Yanagisawa, O. Nureki, M. Kikkawa, K. Harano, R. Shang, E. Nakamura
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Journal Title
Bull. Chem. Soc. Jpn.
Volume: 93
Pages: in press
DOI
Peer Reviewed / Open Access
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