Mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes with C4 chirality: synthesis, resolution, and absolute configuration assignment.
Mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes [HM(III){Pc(alpha-3-OC(5)H(11))(4)}{TOAPP}] [Pc(alpha-3-OC(5)H(11))(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 H(2)Pc(alpha-3-OC(5)H(11))(4) with half-sandwich complexes [M(III)(acac)(TOAPP)], generated in situ from M(acac)(3).nH(2)O and H(2)TAPP [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.
Zhou
Yang
Y
Department of Chemistry, Shandong University, Jinan 250100, China.
Zhang
Yuexing
Y
Wang
Hailong
H
Jiang
Jianzhuang
J
Bian
Yongzhong
Y
Muranaka
Atsuya
A
Kobayashi
Nagao
N
D002851:Chromatography, High Pressure Liquid; D002942:Circular Dichroism; D018360:Crystallography, X-Ray; D008674:Metals, Rare Earth / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D011166:Porphyrins / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
D008674:Metals, Rare Earth; D009942:Organometallic Compounds; D011166:Porphyrins