Reaction of Silyl radicals within a Porphyrin π-Cloud
卟啉 π 云中甲硅烷基的反应
基本信息
- 批准号:11650883
- 负责人:
- 金额:$ 1.86万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (C)
- 财政年份:1999
- 资助国家:日本
- 起止时间:1999 至 2000
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
A series of organosilicon porphyrins) with alkyl (sp^3), alkenyl, aryl (sp^2), and alkynyl (sp), groups at the axial positions were synthesized. Upon irradiation with visible light, dialkylsilicon porphyrins reacted with nitroxy compounds, such as TEMPO to give dinitroxysilicon porphyrins. In the absence of nitroxy compounds, photolysis resulted in the formation of a long-lived (>50 days at 25℃) EPR-active silicon diradical with a g-value of 2.0026, which did not react with nitroxy compounds in the dark but was smoothly trapped by TEMPO to give dinitroxysilicon complex upon excitation with visible light. Irradiation of the dinitroxysilicon with visible light in the presence of free nitroxy compoundss resulted in reversible axial ligand exchange, which proceeded in response to the switching-on and-off of the light, to reach an equilibrium.
合成了一系列轴向含有烷基、烯基、芳基和炔基的有机硅卟啉化合物。在可见光照射下,二烷基硅卟啉与硝基氧基化合物如克里思反应,得到二硝基氧基硅卟啉。在没有硝酰化合物存在的情况下,光解导致形成长寿命(在25℃下>50天)的EPR活性硅双自由基,g值为2.0026,其在黑暗中不与硝酰化合物反应,但在可见光激发下被克里思顺利捕获,得到二硝酰硅复合物。在自由硝氧基化合物的存在下,用可见光照射二硝氧基硅导致可逆的轴向配体交换,其响应于光的开关而进行,以达到平衡。
项目成果
期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
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KONISHI Katsuaki其他文献
KONISHI Katsuaki的其他文献
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{{ truncateString('KONISHI Katsuaki', 18)}}的其他基金
Luminescence sensing based on guest-associated assembling events of semiconductor clusters
基于半导体簇客体相关组装事件的发光传感
- 批准号:
19350063 - 财政年份:2007
- 资助金额:
$ 1.86万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Synthesis of polyoxometalte-containing calixarene polymer via solid-state polymerization
固相聚合合成含多金属氧酸盐的杯芳烃聚合物
- 批准号:
15350064 - 财政年份:2003
- 资助金额:
$ 1.86万 - 项目类别:
Grant-in-Aid for Scientific Research (B)