Chiral Phthalocyanine with Unambiguous Absolute Molecular Structures for Both Enantiomers

Wang, Kang; Wang, Hailong; Mack, John; Li, Wenjun; Kobayashi, Nagao; Jiang, Jianzhuang

doi:10.6023/a12050262

Cited by 10 publications

(5 citation statements)

References 8 publications

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“…The chiral phthalocyaninato zinc complex [Zn{Pc(OBNP) 4 }] ( 1 ) was synthesized in relatively good yield from the cyclic tetramerization of ( R )‐ and ( S )‐dicarbonitrile precursors8 in refluxing n ‐pentanol in the presence of Zn(OAc) 2 ⋅2 H 2 O promoted by 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU). In addition to the molecular ion for the monomeric species [ M ] + , the MALDI‐TOF mass spectrum of 1 also contains intense signal of a dimeric ion [2 M ] + , revealing the relatively high stability of the dimeric entity.…”

Section: Methodsmentioning

confidence: 99%

A Chiral Phthalocyanine Dimer with Well‐Defined Supramolecular Symmetry Based on π–π Interactions

Wang

et al. 2012

Chemistry A European J

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Section: Methodsmentioning

confidence: 99%

A Chiral Phthalocyanine Dimer with Well‐Defined Supramolecular Symmetry Based on π–π Interactions

Wang

et al. 2012

Chemistry A European J

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“…However, the analysis of the diffraction data of single crystals obtained from a CHCl3 solution of enantiopure Zn-1 previously described by Jiang and coworkers also revealed the exclusive presence of dimeric aggregates in the solid state [18]. Analogous results were obtained in the solid state for the enantiopure free base phthalocyanine H2-1 [24].…”

Section: Thermodynamic Characterization Of the Dimerization Process Omentioning

confidence: 57%

“…Synthesis of Zn-1: Chiral phthalocyanines (R)-and (S)-Zn-1 ( Figure 1) and the enantiomerically pure (R)and (S)dinitriles precursors were synthesized following reported procedures [18,24]. The circular dichroism (CD) spectra of the prepared dinitriles, not reported in the original paper, showed, as expected, bisignated CD spectra due to the exciton coupling between the chromophores (naphthyls) present in the molecule.…”

Section: Resultsmentioning

confidence: 82%

Study of the coordination of quinuclidine to a chiral zinc phthalocyanine dimer

Giménez-Agulló

Aragay

Galán‐Mascarós

et al. 2016

J. Porphyrins Phthalocyanines

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We attempted the calculation of an accurate equilibrium constant for the dimerization process of enantiomerically pure Zn-1 using UV-vis dilution experiments. At millimolar concentration Zn-1 is involved in a chemical exchange process between its monomeric and dimeric state that is slow on the 1H NMR timescale. We performed variable-temperature 1H NMR experiments in CDCl3 solution to determine the dimerization constant value at different temperatures and performed a van’t Hoff plot to derive the thermodynamic parameters of the process. The calculated thermodynamic data revealed that the dimerization process is entropy-driven and enthalpically opposed. We also probed the coordination of quinuclidine, 1-azabicyclo[2.2.2]octane, 2, to the Zn-1 using UV-vis and 1H NMR titrations in CDCl3 solution. At micromolar concentration the Zn-1 exclusively exists in solution as a monomer and forms a simple 1:1, [Formula: see text], complex with quinuclidine having a stability constant of [Formula: see text]([Formula: see text]) [Formula: see text] 106 M[Formula: see text]. On the other hand, the 1H NMR titrations carried out at 298 K and at millimolar concentration showed that Zn-1 was present in solution as the dimer and formed 1:2, [Formula: see text], and 2:2, [Formula: see text] complexes by coordination to 2. In addition, the 1:1 complex, [Formula: see text] showed a reduced dimerization constant compared to the uncoordinated parent monomer Zn-1. At high quinuclidine concentration, the 1:1 complex, [Formula: see text], derived from the coordinated dimer dissociation was also detected. The 1H NMR spectra of the titrations displayed separate signals for some hydrogen atoms of the Zn-phthalocyanine in each one of the four species. Remarkably, the chemical exchange processes involving free and bound quinuclidine in the monomeric and dimeric complexes showed different kinetics on the NMR timescale.

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“…Figure 1 summarizes the structures grouped into this category (in the case of 3D-structures, 6-11, only R-enantiomers which have an anti-clockwise binaphthyl structure are shown). In 2012, the synthesis of compound 1 from precursor a was reported (Wang et al, 2012). Previously, similar compounds 4 had been reported from a precursor containing sulfur instead of oxygen in a (i.e., a ′ ) (Kobayashi et al, 1999a) due to the then-known low racemization probability of a' under the experimental conditions.…”

Section: Introductionmentioning

confidence: 73%

“…270-700 nm) for metal-free (top) and zinc (bottom) derivatives of 5, and (D) magnet-chiral dichroism spectra of 10. Adapted from Kobayashi (2012) and Wang et al (2012Wang et al ( , 2014.…”

Section: Spectroscopic Propertiesmentioning

confidence: 99%

Recent Progress in Optically-Active Phthalocyanines and Their Related Azamacrocycles

2020

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Optically-active phthalocyanines (Pcs) and related macrocycles reported in the 2010-2020 period are introduced in this review. They are grouped into several categories: (1) chiral binaphthyl-containing Pcs, (2) optically active alkyl chain-containing Pcs, (3) chiral axial ligand-coordinated or-linked Pcs, (4) chiral subphthalocyanines (SubPcs), and (5) related azamacrocycles. For each compound, the structure and important characteristics are summarized.

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Chiral Phthalocyanine with Unambiguous Absolute Molecular Structures for Both Enantiomers

Cited by 10 publications

References 8 publications

A Chiral Phthalocyanine Dimer with Well‐Defined Supramolecular Symmetry Based on π–π Interactions

A Chiral Phthalocyanine Dimer with Well‐Defined Supramolecular Symmetry Based on π–π Interactions

Study of the coordination of quinuclidine to a chiral zinc phthalocyanine dimer

Recent Progress in Optically-Active Phthalocyanines and Their Related Azamacrocycles

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