Charge-Transfer Salts of Electron-Rich Diruthenium and Macrocyclic Tetraruthenium Complexes

本项目的目的是合成和详细表征具有扩展的pi共轭连接体的双核和大环四铀配合物及其电荷转移盐。当与合适的强有机电子受体如四卤代苯醌X4BQ或四氰基对喹二甲烷TCNQ和F4TCNQ结合时，这些络合物的结构和电子条件要求生成具有pi堆叠结构的导电电荷转移盐。特别是，我们将研究所得到的电荷转移盐的电离性(即施主/受主的正负电荷比例)以及它们的光学、电子和磁性。我们将通过分析Ru(CO)给电子体的振动能和有机受体的CO和CN伸缩频率的变化，以及通过对其电子光谱和电子顺磁共振光谱中电荷转移带的加固，来获得关于有机金属给体和有机受体之间电荷转移程度的详细信息。我们还将讨论电荷转移盐的电离性和结构如何依赖于给体和受体的化学计量比及其本征氧化还原电位这一重要问题。

The aim of this project is the synthesis and detailed characterisation of dinuclear and macrocyclic tetraruthenium complexes with expanded, pi-conjugated linkers and of their charge transfer salts. These complexes are constructed such as to entail the structural and electronic prerequisites for generating electrically conductive charge transfer salts with pi-stacked structures when combinded with appropriate strong organic electron acceptors such as tetrahalogenated bezoquinones X4BQ or tetracyano-para-quinodimethanes TCNQ and F4TCNQ. In particular, we will investigate the resulting charge-transfer salts with respect to their ionicity (i. e. the fraction of positive / negative charge at the donor / acceptor) and their optical, electronic and magnetic properties. We will obtain detailed information as to the extent of charge transfer between the organometallic donor and the organic acceptor by analyzing the changes of the Ru(CO) vibrational energies of the ruthenium alkenyl donors and of the CO and CN stretching frequencies of the organic acceptor as well as by srutinizing the charge transfer bands in their electronic spectra and electronic paramagnetic resonance spectra. We will also address the important question of how the ionicities and structures of the charge transfer salts depend on the stoichiometric ratio of the donor and the acceptor and their intrinsic redox potentials.