Flores-Torres Samuel, Hutchison Geoffrey R, Soltzberg Leonard J, Abruña Héctor D
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, USA.
J Am Chem Soc. 2006 Feb 8;128(5):1513-22. doi: 10.1021/ja0552139.
We have prepared and characterized a series of multimetallic oligomers of Ru using the pi-conjugated bridging ligand tetra-2-pyridyl-1,4-pyrazine (tppz), as well as mixed-ligand complexes with terpyridine end caps, and analyzed their electrochemical and spectroscopic properties, comparing them with modern computational electronic structure methods. The results suggest that the high degree of metal-metal interunit communication in these linear oligomers yields low HOMO-LUMO gaps, high delocalization, and the onset of "quasi-band" features, all indicative that these compounds should be excellent molecular wire materials. Recent spectroscopic and excited-state analyses of these and related compounds focus on optically accessible states, which ignore optically silent frontier electronic states more relevant to nanoelectronic applications.
我们制备并表征了一系列使用π共轭桥连配体四-2-吡啶基-1,4-吡嗪（tppz）的钌多金属低聚物，以及带有三联吡啶端基的混合配体配合物，并分析了它们的电化学和光谱性质，同时将其与现代计算电子结构方法进行比较。结果表明，这些线性低聚物中高度的金属-金属单元间通讯产生了低的最高占据分子轨道-最低未占据分子轨道能隙、高离域性以及“准能带”特征的出现，所有这些都表明这些化合物应该是优异的分子导线材料。最近对这些及相关化合物的光谱和激发态分析集中在光学可及态上，而忽略了与纳米电子应用更相关的光学沉默前沿电子态。
