10.1021/ja905284d.s002 Luciano Cuesta Luciano Cuesta Elizabeth Karnas Elizabeth Karnas Vincent M. Lynch Vincent M. Lynch Ping Chen Ping Chen Jing Shen Jing Shen Karl M. Kadish Karl M. Kadish Kei Ohkubo Kei Ohkubo Shunichi Fukuzumi Shunichi Fukuzumi Jonathan L. Sessler Jonathan L. Sessler Metalloporphycenes: Synthesis and Characterization of (Pentamethylcyclopentadienyl)ruthenium Sitting-Atop and π-Complexes American Chemical Society 2009 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 2009-09-23 00:00:00 Dataset 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.