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Physical and chemical properties of 1B metal atoms in condensed matter

凝聚态物质中1B金属原子的物理和化学性质

基本信息

批准号：
13650885
负责人：
MIYATAKE Yoko
金额：
$ 1.6万
依托单位：
OSAKA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

Magnetic and optical properties of 1B metals produced radiation-chemically by reducing their mono cations in condensed matters have been investigated as a fundamental research to elucidate the function and effects of metal ions and/or metal atoms in biological systems.Au^0 was produced at 77 K by γ-irradiation of MTHF solutions containing Au^+. The absorption bands at around 270-280 nm and 340 nm were ascribed to Au^0 in the solid solutions. The weak absorption band at around 420 nm was also attributed to Au^0. These bands were red-shifted and broadened compared to those in the rare gas matrixes, indicating a strong solvent-Au^0 interaction. Excitation of the absorption bands with light of wavelengths of 280 nm led to phosphorescence of three kinds of lifetimes. One of them with lifetime of about 625 ms was attributed to type of exciplex as (Au^+・Ln)^*. As for other two oomponents with lifetime of about 146 and 461 ms, it became clear from the behavior of the time dependence profile of … More the phosphorescence intensity that the latter grew as the former decayed. These were ascribed to such types of exciplex as (Au^0・Ln …Au^+)^* and (Au^+…Ln・Au^0)^*, respectively. The absorption band, which was ascribed to a photoionization of Au^0, must be around at 280 nm. The fluorescence band observed at 385 nm and a set of bands at 480, 520 and 580 nm bear close resemblance to the E_1 and E_2 bands of Ag^0, respectively. The former was attributed to the exciplex (Au^0・Ln …Au^+)^* that was not paramagnetic species. The latter was attributed to the exciplex (Au^0・Ln)^*. A group of the emission bands with peaks at 456, 482, 484 and 520 nm which had the characteristic structure of the minor image relations with the absorption bands of Au^0, in the gas phase and the solid rare gas phase. This structural profile was observed for the first time in the present study for Au^0 produced in γ-irradiated organic solid solutions at 77 K. These were attributed to Au^0 trapped in a large cavity where Au^0 in its excited state interacts very weakly with the surrounding solvent molecules. Less

通过在凝聚态物质中还原其单阳离子辐射化学法制备的1B金属的磁性和光学性质，作为阐明金属离子和/或金属原子在生物系统中的功能和作用的基础研究。含Au^+的MTHF溶液在77 K时经γ辐照产生Au^0。在270 ~ 280 nm和340 nm处的吸收波段归属于固溶体中的Au^0。在420 nm附近的弱吸收带也归因于Au^0。与稀有气体基质相比，这些谱带红移和变宽，表明溶剂- au ^0相互作用强。用波长为280 nm的光激发吸收带可产生三种寿命的磷光。其中一个寿命约为625 ms，其外络合物类型为（Au^+·Ln）^*。对于寿命分别为146 ms和461 ms的其他两种组分，从其荧光强度的时间依赖谱的行为可以清楚地看出，后者随着前者的衰减而增长。这分别归因于（Au^0·Ln…Au^+）^*和（Au^+…Ln·Au^0）^*。由于Au^0的光离作用，吸收带一定在280nm附近。385 nm处的荧光带和480、520、580 nm处的一组荧光带分别与Ag^0的E_1和E_2波段非常相似。前者归因于非顺磁性的外络合物（Au^0·Ln…Au^+）^*。后者归因于外络合物（Au^0·Ln）^*。在气相和固体稀有气相中，一组峰值为456,482,484和520 nm的发射带与Au^0的吸收带具有小像关系的特征结构。本研究首次观察到γ辐照有机固溶体在77 K下产生的Au^0的这种结构。这是由于Au^0被困在一个大的腔中，Au^0处于激发态，与周围的溶剂分子相互作用非常弱。少