title: Metalloporphycenes: synthesis and characterization of (pentamethylcyclopentadienyl)ruthenium sitting-atop and pi-complexes.
abstract: Unprecedented porphycene complexes, containing a [RuCp*] (Cp*: pentamethylcyclopentadienyl) fragment accommodated in the central N(4) core or directly bonded to the "pi-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.
authors.affiliation: Department of Chemistry & Biochemistry, University Station-A5300, The University of Texas, Austin, Texas 78712-0165, USA.
authors.forename: Luciano
authors.initials: L
authors.lastname: Cuesta
authors.forename: Elizabeth
authors.initials: E
authors.lastname: Karnas
authors.forename: Vincent M
authors.initials: VM
authors.lastname: Lynch
authors.forename: Ping
authors.initials: P
authors.lastname: Chen
authors.forename: Jing
authors.initials: J
authors.lastname: Shen
authors.forename: Karl M
authors.initials: KM
authors.lastname: Kadish
authors.forename: Kei
authors.initials: K
authors.lastname: Ohkubo
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.forename: Jonathan L
authors.initials: JL
authors.lastname: Sessler