%0 Journal Article %A Cuesta, Luciano %A Karnas, Elizabeth %A Lynch, Vincent M. %A Chen, Ping %A Shen, Jing %A Kadish, Karl M. %A Ohkubo, Kei %A Fukuzumi, Shunichi %A Sessler, Jonathan L. %D 2009 %T Metalloporphycenes: Synthesis and Characterization of (Pentamethylcyclopentadienyl)ruthenium Sitting-Atop and π-Complexes %U https://acs.figshare.com/articles/journal_contribution/Metalloporphycenes_Synthesis_and_Characterization_of_Pentamethylcyclopentadienyl_ruthenium_Sitting_Atop_and_Complexes/2826328 %R 10.1021/ja905284d.s001 %2 https://acs.figshare.com/ndownloader/files/4524019 %K Ni %K laser flash photolysis %K macrocycle %K calculation %K metal centers %K N 4 core %K EPR spectra %K lifetime %K Metalloporphycene %K Pentamethylcyclopentadienyl %K ComplexesUnprecedented %K moiety %K complex %K communication %K Synthesi %K fragment %K compound %K pentamethylcyclopentadienyl %K species %K electrochemical properties %K porphycene derivatives %K ruthenocene unit %K fluorescence %K Characterization %K RuCp %K diffraction %K analysis %K crystal %K Cp %K photoinduced electron transfer %K Cu %X 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. %I ACS Publications