Effects of Environment on Intramolecular Electron Transfer in Mixed‐valence 1′,1‴‐Dinaphthylmethyl(biferrocenium) Triiodide: Structural and 57Fe Mössbauer Characteristics
Effects of Environment on Intramolecular Electron Transfer in Mixed‐valence 1′,1‴‐Dinaphthylmethyl(biferrocenium) Triiodide: Structural and 57Fe Mössbauer Characteristics
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环境对混合价 1′,1‴-二萘甲基（联二茂鎓）三碘化物分子内电子转移的影响：结构和 57Fe 穆斯堡尔特性
DOI：
10.1002/anie.199720021
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发表时间：
1997
影响因子：
--
通讯作者：
Kuan
中科院分区：
文献类型：
--
作者：
T. Dong;X. Lai;Zhi‐Wei Lin;Kuan
在过去的几年里，化学和生物体系中的电子转移[2]受到了相当大的关注。最近对混合价双二茂铁配合物1-6中电子转移的研究表明，阳离子周围的环境可能是决定分子内电子转移速率的最重要因素。配合物1-6给出了不寻常的温度依赖的穆斯堡尔谱。[4]在低于77 K的温度下，它们每个都显示出两个双峰，一个用于Fe”，一个用于Fe“'位置（电子转移速率<10 ~ 7 sI）。在每一种情况下，两个双峰在温度升高时一起移动，最终变成一个单一的”平均价“双峰。Hendrickson等人认为穆斯堡尔谱的温度依赖性是由于与三碘反离子和烷基取代基有关的晶格动力学的开始。[~ 1]在低温（< 100 K）下，配合物晶格的所有部分都是静态的。随着温度的升高，所形成的热能可能足以触发晶体中的协同相变。在1-6中没有观察到晶体相变;我们认为这种相变可以用随温度的逐渐（二级）变化来描述。1 x =2 x=3 x=
Electron transfer in chemical''] and biological [2] systems has received considerable attention in the last few years. Recent studies of electron transfer in mixed-valence biferrocenium complexes 1-6 revealed that the environment surrounding a cation is perhaps the most important factor in determining the rate of intramolecular electron transfer.['" 31 Complexes 1-6 give unusual temperature-dependent Mossbauer spectra.[4] At temperatures below 77 K they each show two doublets, one for the Fe" and one for the Fe"'site (electron-transfer rate< lo7 sI). In each case the two doublets move together upon increasing temperature and eventually become a single" average-valence''doublet. Hendrickson et al. suggested that the temperature dependence of the Mossbauer spectrum is due to the onset of lattice dynamics associated with the triiodide counterions and alkyl s~ bstituents.[~ l At low temperatures (< 100 K) all parts of the crystal lattice of the complex are static. As the temperature is increased, the thermal energy formed could be sufficient to trigger a cooperative phase transition in the crystal A crystallographic phase change was not observed in 1-6; we believe that the transition may be described in terms of a gradual (second-order) change with temperature. lx=2 x=3 x=