1999 Fiscal Year Final Research Report Summary
Reversible chlorine-gas uptake and release system with transition-metal polypyrazolyborate complexes and its utilization and development as a solid-state gas-sensor
| Project/Area Number |
10650812
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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 |
工業物理化学
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| Research Institution | Nagasaki University |
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Principal Investigator |
ONISHI Masayoshi Nagasaki University, Faculty of Engineering, Professor, 工学部, 教授 (00039695)
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| Co-Investigator(Kenkyū-buntansha) |
MUTO Norio Engineering and Research Division, Sogo Security Services Co. Ltd. Head Research Manager, 技術研究所, 所長(研究職)
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| Project Period (FY) |
1998 – 1999
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| Keywords | chlorine gas / ruthenium / polypyrazolylborate / gas sensor / single crystal X-ray analysis |
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| Research Abstract |
Uninegative polypyrazolylborates [BRpzィイD23ィエD2]ィイD1-ィエD1 (pz=1-pyrazolyl) serve as sterically bulky tridentate ligands on complexation with transition-metal and rare-earth elements. In view of easy access to substituted pyrazoles, introduction of various substituents has been carried out into the pyrazolyl rings of this tripodal ligand system in these years, with the hope of fine-tuning the electronic and steric properties of reaction fields built up on the central metal ions in the complexes.
(1) Electrophilic substitution of bromine on pyrazoles and bis(polypyrazolylborato)nickel(II).
Reactions of pyrazoles with bromine molecules gave bromic acid salts of 4-bromopyrazoles. Similar reactions of bis(olypyrazolylborato)nickel(II) afforded a mixture of [Ru { BH(pz)ィイD2nィエD2(4-Brpz)ィイD2(3-n)ィエD2} {BH(pZ)ィイD2mィエD2 (4- Brpz)ィイD2(3-m)ィエD2}] through electrophilic substitution process. However, similar electrophilic process did not proceed in the nickel(II) complexes with 4-Br-substituted pyraz
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olyl rings.
(2) Syntheses and characterization of bis(polypyrazolylborato)ruthenium(II) complexes.
Bis(polypyrazolylborato)ruthenium(II)complexes were prepared, which involve a variety of substituents on the pyrazolyl rings. We performed structural characterization with single-crystal X-ray analyses, evaluation of electronic properties of substituted polypyrazolylborate ligands on complexation, formation of charge-transfer species of the ruthenium(II) complexes with halogenated hydrocarbon solvents and photoinduced electron-transfer reactions, and characterization of the bis(polypyrazolylborato)ruthenium(II) species formed.
(3) Reactions of bis(substituted polypyrazolylborato)ruthenium(II) complexes in the solid state with gaseous chlorine molecules.
Microcrystalline powder of bis(substituted polypyrazolylborato)ruthenium(II) with various substituents, such as 4-methyl groups on the pyrazolyl rings, was treated with chlorine gas, and we found reversible chlorine-gas uptake and release system. Their diffuse reflectance spectrometry was run to observe clear color-change by reversible chlorine-gas uptake linked with the Ru(III)/(II) redox couple, which confirmed the retention of the developable potentiality as a solid-state chlorine-gas sensor. Less
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Research Products
(2 results)
