Metalloporphycenes: Synthesis and Characterization of (Pentamethylcyclopentadienyl)ruthenium Sitting-Atop and π-Complexes Luciano Cuesta Elizabeth Karnas Vincent M. Lynch Ping Chen Jing Shen Karl M. Kadish Kei Ohkubo Shunichi Fukuzumi Jonathan L. Sessler 10.1021/ja905284d.s002 https://acs.figshare.com/articles/dataset/Metalloporphycenes_Synthesis_and_Characterization_of_Pentamethylcyclopentadienyl_ruthenium_Sitting_Atop_and_Complexes/2826331 Unprecedented porphycene complexes, containing a [RuCp*] (Cp*: pentamethylcyclopentadienyl) fragment accommodated in the central N<sub>4</sub> 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. 2009-09-23 00:00:00 Ni laser flash photolysis macrocycle calculation metal centers N 4 core EPR spectra lifetime Metalloporphycene Pentamethylcyclopentadienyl ComplexesUnprecedented moiety complex communication Synthesi fragment compound pentamethylcyclopentadienyl species electrochemical properties porphycene derivatives ruthenocene unit fluorescence Characterization RuCp diffraction analysis crystal Cp photoinduced electron transfer Cu