Mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes with C4 chirality: Synthesis, resolution, and absolute configuration assignment

Yang Zhou, Yuexing Zhang, Hailong Wang, Jianzhuang Jiang, Yongzhong Bian, Atsuya Muranaka, Nagao Kobayashi

Research output: Contribution to journalArticlepeer-review

35 Citations (Scopus)

Abstract

Mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes [HMIII{Pc(α-3-OC5H11)4}{TOAPP} ] [Pc(α-3-OC5H11)4 = 1,8,15,22- tetrakis(3-pentyloxy)-phthalocyaninate; TOAPP = meso-tetrakis(4-octylamino- phenyl)porphyrinate; M = Y (1), Ho (2)] were prepared as a racemic mixture by treating metal-free phthalocyanine H2Pc(α-3-OC 5H1)4 with half-sandwich complexes [M III(acac)(TOAPP)], generated in situ from M(acac)3- nH2O and H2TAPP [TAPP = meso-tetrakis(4-amino-phenyl) porphyrinate], in refluxing 1-octanol. The obtained double-deckers were characterized by elemental analysis and various spectroscopic methods. The molecular structures of 1 and 2 were determined by single-crystal X-ray diffraction analysis. The compounds crystallize in the triclinic system with a pair of enantiomeric double-deckers per unit cell. Resolution of 1 and 2 was achieved using a chiral HPLC technique combined with the formation of their diastereomeric mixture using L-Boc-Phe-OH as the chiral resolving agent, yielding for the first time the pure diastereoisomers of chiral mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes with C 4 symmetry. The absolute configuration of these chiral complexes was assigned by comparing the experimental circular dichroism spectrum with a simulated one on the basis of time-dependent density functional theory calculations.

Original languageEnglish
Pages (from-to)8925-8933
Number of pages9
JournalInorganic chemistry
Volume48
Issue number18
DOIs
Publication statusPublished - 2009 Sep 21

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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