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