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

Wang, Kang; Qi, Dongdong; Wang, Hailong; Cao, Wei; Li, Wenjun; Jiang, Jianzhuang

doi:10.1002/chem.201202888

Cited by 28 publications

(16 citation statements)

References 45 publications

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“…Enantiopure Zn-1 was isolated in acceptable yields (39-45 %) after silica column chromatography purification of the reaction crude using CH2Cl2:THF (100:2) as eluent mixture. As expected, both enantiomers presented identical 1 H NMR and UV-vis spectra that were in agreement with the ones previously reported by Jiang and co-workers [18].…”

Section: Resultssupporting

confidence: 92%

“…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: 80%

“…The aggregation of zinc-phthalocyanines is known to occur in solution even at the low concentrations used to register their UV-vis spectra [18]. The UV-vis spectrum of enantiopure Zn-1 in CHCl3 solution at a 10 -6 M concentration displayed the typical absorption bands of a metallated phthalocyanine (i.e.…”

Section: Thermodynamic Characterization Of the Dimerization Process Omentioning

confidence: 99%

“…The most widely synthetic approach used consists on the introduction of chiral residues into the macrocycle's periphery. Chiral phthalocyanine Zn-1 (Figure 1) was reported in 2012 by Jiang and coworkers [18]. It constitutes a nice example of building an enantiomerically pure Pc through peripheral decoration with chiral binaphtyl units.…”

Section: Introductionmentioning

confidence: 97%

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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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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 80%

Section: Thermodynamic Characterization Of the Dimerization Process Omentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

See 2 more Smart Citations

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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“…To further clarify the formation of the face-to-face Zn(Por)-anthraquinone dimer in solution, theoretical calculations of the p-p interaction between [ZnA C H T U N G T R E N N U N G (TPP)] (TPP = dianion of tetraA C H T U N G T R E N N U N G (phenyl)porphyrin) and anthraquinone on the basis of the optimized structure were conducted by DFT methods at the wb97xd level of theory. [20] The computational results reveal a high [ZnA C H T U N G T R E N N U N G (TPP)]-anthraquinone p-p interaction energy, [21] 55.6 kcal mol À 1 , which seems to be responsible for the formation of the dimeric entity. Nevertheless, the red-shift observed for the Soret absorption band of ZnA C H T U N G T R E N N U N G (Por) upon titration with anthraquinone is also well reproduced by the time-dependent DFT (TDDFT) calculations ( Table S5 in the Supporting Information).…”

mentioning

confidence: 99%

Porphyrin‐POSS Molecular Hybrids

Sun

Chen

Zhao

et al. 2013

Chemistry A European J

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Porphyrin-POSS hybrid: Porphyrin-POSS molecular hybrid composites (see scheme; POSS = polyhedral oligomeric silsesquioxanes) were synthesized and structurally characterized, allowing the realization of truly homogenous dispersion of basic functional building blocks between organic and inorganic components at the molecular level. These materials allow the optimization of aggregation/association behavior and thus the functional optical properties of the porphyrinato zinc compounds.

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Unsymmetrical Pyrene‐Fused Phthalocyanine Derivatives: Synthesis, Structure, and Properties

Pan

Chen

Wang

et al. 2015

Chemistry A European J

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Novel pyrene-fused unsymmetrical phthalocyanine derivatives 2,3,9,10,16,17-hexakis(2,6-dimethylphenoxy)-22,25-diaza(2,7-di-tert-butylpyrene)[4,5]phthalocyaninato zinc complex Zn[Pc(Pz-pyrene)(OC8 H9 )6 ] (1) and 2,3,9,10-tra(2,6-dimethylphenoxy)-15,18,22,25-traza(2,7-di-tert-butylpyrene)[4,5]phthalocyaninato zinc compound Zn[Pc(Pz-pyrene)2 (OC8 H9 )4 ] (2) were isolated for the first time. These unsymmetrical pyrene-fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods. In particular, the pyrene-fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X-ray diffraction analysis of 1, representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene.

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

Cited by 28 publications

References 45 publications

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

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

Porphyrin‐POSS Molecular Hybrids

Unsymmetrical Pyrene‐Fused Phthalocyanine Derivatives: Synthesis, Structure, and Properties

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