title: Synthesis and Characterization of Rare Earth Corrole-Phthalocyanine Heteroleptic Triple-Decker Complexes.
abstract: We recently reported the first example of a europium triple-decker tetrapyrrole with mixed corrole and phthalocyanine macrocycles and have now extended the synthetic method to prepare a series of rare earth corrole-phthalocyanine heteroleptic triple-decker complexes, which are characterized by spectroscopic and electrochemical methods. The examined complexes are represented as M2[Pc(OC4H9)8]2[Cor(ClPh)3], where Pc = phthalocyanine, Cor = corrole, and M is Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), or Tb(III). The Y(III) derivative with OC4H9 Pc substituents was obtained in too low a yield to characterize, but for the purpose of comparison, Y2[Pc(OC5H11)8]2[Cor(ClPh)3] was synthesized and characterized in a similar manner. The molecular structure of Eu2[Pc(OC4H9)8]2[Cor(ClPh)3] was determined by single-crystal X-ray diffraction and showed the corrole to be the central macrocycle of the triple-decker unit with a phthalocyanine on each end. Each triple-decker complex undergoes up to eight reversible or quasireversible one-electron oxidations and reductions with E1/2 values being linearly related to the ionic radius of the central ions. The energy (E) of the main Q-band is also linearly related to the radius of the metal. Comparisons are made between the physicochemical properties of the newly synthesized mixed corrole-phthalocyanine complexes and previously characterized double- and triple-decker derivatives with phthalocyanine and/or porphyrin macrocycles.
authors.affiliation: †School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Peoples Republic of China.|‡Department of Chemistry, University of Houston, Houston, Texas 77204-5003 United States.
authors.forename: Guifen
authors.initials: G
authors.lastname: Lu
authors.affiliation: †School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Peoples Republic of China.
authors.forename: Jing
authors.initials: J
authors.lastname: Li
authors.affiliation: †School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Peoples Republic of China.
authors.forename: Sen
authors.initials: S
authors.lastname: Yan
authors.affiliation: †School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Peoples Republic of China.
authors.forename: Weihua
authors.initials: W
authors.lastname: Zhu
authors.affiliation: †School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Peoples Republic of China.
authors.forename: Zhongping
authors.initials: Z
authors.lastname: Ou
authors.affiliation: ‡Department of Chemistry, University of Houston, Houston, Texas 77204-5003 United States.
authors.forename: Karl M
authors.initials: KM
authors.lastname: Kadish