Reversible chlorine-gas uptake and release system with transition-metal polypyrazolyborate complexes and its utilization and development as a solid-state gas-sensor

Uninegative polypyrazolylborates [BRpz D23 - D2] BRpz =1-pyrazolyl serve as sterically bulkytridentate ligands on complexation with transition-metal and rare-earth elements. In view of easy访问substituted pyrazoles，introduction of various substituents has been carried out into the pyrazolyl rings of this tripodalligand system in these years，the hope of fine-tuning the electronic and steric properties of reaction fields built up on thecentral metal ions in the complexes.(1) Electrophilic substitution of bromine on pyrazoles and Electrophilic substitutionbis(polypyrazolylborato)nickel(II).Reactions of pyrazoles with bromine molecules gave bromic acidsalts of 4-bromopyrazoles. Similar reactions of bis(olypyrazolylborato)nickel(II) afforded a mixtureof [Ru {BH(pz) d - 2n d - D2(4-Brpz) d - D2(3-n) d - D2} {BH(pz) d - 2m d - D2(4-Brpz) d - D2(3-m) d - D2}] throughelectrophilic substitution process. Howeversimilar electrophilic process did not proceed in the nickel(II) complexes with 4- bru -substitutedpyraz……More olyl rings.(2) Syntheses and characterization of bis(polypyrazolylborato)ruthenium（II）complexes. bis (polypyrazolylborato)ruthenium(II)complexes were preparedwhich involve a variety of substituents on the pyrazolyl rings. We performed结构characterization with single-crystal X-ray analysesevaluation of electronic properties of substituted polypyrazolylborate ligands on complexationformation of charge-transfer species of the ruthenium(II) complexes with halogenated hydrocarbonsolvents and photoinduced electron-transfer reactionsand characterization of the bis(polypyrazolylborato)ruthenium(II) species form .(3) Reactions ofbis(substituted polypyrazolylborato)ruthenium(II) complexes in the solid state with gaseous chlorinemolecules.microcrystalline powder of bis (substituted polypyrazolylborato) ruthenium (ii) with varioussubstituents, such as 4-methyl groups on the pyrazolyl rings, was treated with chlorine gas我们发现了reversible chlorine-gas uptake and release system.他们的差异反射spectrometry was run to observe clear color-change by reversible chlorine-gas uptake linked with theRu(III)/(II) redox couple这是一个可开发的潜力作为一个solid-state chlorine-gas sensor.less

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 … More 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