Metalloporphycenes: Synthesis and Characterization of (Pentamethylcyclopentadienyl)ruthenium Sitting-Atop and π-Complexes

Unprecedented porphycene complexes, containing a [RuCp*] (Cp*: pentamethylcyclopentadienyl) fragment accommodated in the central N4 core or directly bonded to the “π-face” of the macrocycle have been prepared and fully characterized, including via single crystal X-ray diffraction analysis. The optical and electrochemical properties of these new families of compounds were examined in detail, revealing fluorescence in the case of the “sitting-atop” complexes for which the lifetime was determined. For both metal (M = Cu, Ni) porphycene derivatives with a “fused” ruthenocene moiety, strong electronic communication was observed through efficient photoinduced electron transfer from the ruthenocene unit to the macrocycle after laser flash photolysis, affording a charge-separated state. This ruthenocene-macrocycle communication was also confirmed by observation of strong spin−spin coupling in the EPR spectra of the one-electron oxidized species; this allowed for calculation of the distance between the two metal centers.

创纪录的紫罗兰色复合物已被制备并进行了全面表征，其中包含一个嵌入于中央N4核或直接连接到宏环“π面”的[RuCp*]（Cp*: 五甲基环戊二烯基）片段。通过单晶X射线衍射分析等方法，对这些复合物的光学和电化学性质进行了深入研究。在“位于上方”的复合物中，观察到荧光现象，并确定了其寿命。对于具有“融合”型钌配合物的金属（M = Cu, Ni）紫罗兰衍生物，观察到从钌配合单元到宏环的强电子通信，这是通过激光闪光光解诱导的电子转移实现的，从而产生了电荷分离状态。这种钌配合物与宏环之间的通信亦通过观察单电子氧化物种的EPR谱中的强自旋-自旋偶合得到证实；这有助于计算两个金属中心之间的距离。