Xu Shuang, Smith James E T, Gozem Samer, Krylov Anna I, Weber J Mathias
Department of Chemistry, University of Southern California , Los Angeles, California 90089-0482, United States.
Inorg Chem. 2017 Jun 19;56(12):7029-7037. doi: 10.1021/acs.inorgchem.7b00620. Epub 2017 Jun 6.
We measured the electronic spectra of mass-selected [M(bpy)] (M = Fe and Os, bpy = 2,2'-bipyridine) ions in vacuo by photodissociation spectroscopy of their N adducts, [M(bpy)]·N. Extensive band systems in the visible (predominantly charge transfer) and near-ultraviolet (ππ*) spectral regions are reported. The [M(bpy)]·N target ions were prepared by condensing N onto electrosprayed ions in a cryogenic ion trap at ca. 25 K and then mass-selected by time-of-flight mass spectrometry. The electronic photodissociation spectra of the cold, gas-phase ions closely reflect their intrinsic properties, i.e., without perturbation by solvent effects. The spectra are interpreted using time-dependent density functional theory calculations both with and without accounting for relativistic effects.
我们通过对[M(bpy)]·N（M = Fe和Os，bpy = 2,2'-联吡啶）的N加合物进行光解离光谱，在真空中测量了质量选择的[M(bpy)]离子的电子光谱。报道了在可见光（主要是电荷转移）和近紫外（ππ*）光谱区域的广泛能带系统。[M(bpy)]·N目标离子是通过在约25 K的低温离子阱中将N冷凝到电喷雾离子上制备的，然后通过飞行时间质谱进行质量选择。冷的气相离子的电子光解离光谱紧密反映了它们的固有性质，即不受溶剂效应的干扰。使用含时密度泛函理论计算对光谱进行了解释，计算时既考虑了相对论效应，也未考虑相对论效应。
