title: Constructing bis(porphyrinato) rare earth double-decker complexes involving N-confused porphyrin.
abstract: Reaction of metal-free N-confused 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (H2NTClPP) with metal-free 5,10,15,20-tetrakis[(4-tert-butyl)phenyl]porphyrin (H2TBPP) in the presence of M(III)(acac)3·nH2O (acac = acetylacetonate) in refluxing 1,2,4-trichlorobenzene (TCB) led to the isolation of heteroleptic bis(porphyrinato) rare earth compounds M(III)(HNTClPP)(TBPP) (M = La, Pr) (1, 2) in 6.7-10% yield. These represent the first examples of sandwich-type porphyrin rare earth double-decker complexes that involve N-confused porphyrin ligand. Different from their homoleptic bis(porphyrinato) rare earth double-decker counterparts HM(III)(TBPP)2 (M = La, Pr) (3, 4), the acidic proton in the heteroleptic analogues was revealed to localize at the inverted pyrrole nitrogen atom of the N-confused porphyrin ligand on the basis of NMR spectroscopic studies. Nevertheless, their heteroleptic bis(porphyrinato) sandwich molecular nature was confirmed on the basis of single crystal X-ray diffraction analysis over the praseodymium double-decker complex.
authors.affiliation: Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China. jianzhuang@ustb.edu.cn kangwang@ustb.edu.cn.
authors.forename: Yuehong
authors.initials: Y
authors.lastname: Zhang
authors.forename: Wei
authors.initials: W
authors.lastname: Cao
authors.forename: Kang
authors.initials: K
authors.lastname: Wang
authors.forename: Jianzhuang
authors.initials: J
authors.lastname: Jiang