Bis-palladium(II) complex of doubly N-confused octaphyrin(1.1.1.1.1.1.1.1): Möbius aromaticity and chiroptical properties

Basumatary, Biju; Mitsuno, Koki; Ishida, Masatoshi; Furuta, Hiroyuki

doi:10.1142/s1088424619501116

Cited by 11 publications

(5 citation statements)

References 50 publications

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“…Reproduced with permission from refs. [30] and [31]. Copyright (2017) Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim, and (2020) World Scientific Publishing Company, respectively.…”

Section: Strategies For the Chiral Resolution Of Expanded Porphyrinoidsmentioning

confidence: 99%

“…When Pd(OAc) 2 was used in place of Cu(OAc) 2 , a weakly aromatic bis‐palladium(II) complex 11‐Pd 2 was obtained (Figure 11). [31] Complex 11‐Pd 2 was characterized by a Möbius twisted geometry, wherein the two palladium(II) cations were located in NNNN and NNNC coordination cavities. Racemic 11‐Pd 2 could be separated into the corresponding optically pure enantiomers via chiral HPLC (Daicel, Chiralpak IE‐3).…”

Section: Strategies For the Chiral Resolution Of Expanded Porphyrinoidsmentioning

confidence: 99%

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Resolution of Expanded Porphyrinoids: A Path to Persistent Chirality and Appealing Chiroptical Properties

Han,

Sessler

et al. 2023

Chemistry A European J

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Chirality is a fundamental characteristic of nature. Expanded porphyrinoids and their analogues offer an attractive platform for delving into the intricacies of chirality. Expanded porphyrioids comprise pyrrolic macrocycles and related heterocyclic systems. As a class, expanded porphyrioids are widely recognized for their flexible structural features, nontrivial coordination capabilities, and intriguing optical and electronic properties. With limited exceptions, their inherent conformational flexibility coupled with a low racemization barrier allows for the facile interchange between enantiomers. As a result, achieving the effective chiral resolution of individual enantiomers and the subsequent exploration of their chiroptical properties represents a significant challenge. This review summarizes strategies used to realize the chiral resolution of expanded porphyrinoids and the understanding of intrinsic chiroptical properties that has emerged from these separation efforts. It is our hope that this review will serve not only to codify our current understanding of chiral expanded porphyrinoids, but also inspire advances in the generalized area of chiral functional materials.

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“…Reproduced with permission from refs. [30] and [31]. Copyright (2017) Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim, and (2020) World Scientific Publishing Company, respectively.…”

Section: Strategies For the Chiral Resolution Of Expanded Porphyrinoidsmentioning

confidence: 99%

Section: Strategies For the Chiral Resolution Of Expanded Porphyrinoidsmentioning

confidence: 99%

Resolution of Expanded Porphyrinoids: A Path to Persistent Chirality and Appealing Chiroptical Properties

Han,

Sessler

et al. 2023

Chemistry A European J

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“…Upon palladium metalation of doubly N-confused octaphyrin, a conformational change was observed. 422 The treatment of 440 with Pd(OAc) 2 gave the bis-palladium(II) complex 442 in 52% yield (Scheme 173). The bis-palladium(II) complex 442 had a Mobius-type twisted conformation, which showed a weak aromatic character plausibly due to the cross-conjugated electronic structure of the N-confused pyrrole moieties.…”

Section: Doubly N-confused Octaphyrinsmentioning

confidence: 99%

“…Upon palladium metalation of doubly N-confused octaphyrin, a conformational change was observed . The treatment of 440 with Pd(OAc) 2 gave the bis-palladium(II) complex 442 in 52% yield (Scheme ).…”

Section: Confusion In Expanded Porphyrinsmentioning

confidence: 99%

Creation from Confusion and Fusion in the Porphyrin World─The Last Three Decades of N-Confused Porphyrinoid Chemistry

Toganoh

Furuta

2022

Chem. Rev.

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Confusion is a novel concept of isomerism in porphyrin chemistry, delivering a steady stream of new chemistry since the discovery of N-confused porphyrin, a porphyrin mutant, in 1994. These days, the number of confused porphyrinoids is increasing, and confusion and associated fusion are found in various fields such as supramolecular chemistry, materials chemistry, biological chemistry, and catalysts. In this review, the birth and growth of confused porphyrinoids in the last three decades are described.

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“…Five years later, Vogel and collaborators [11] introduced a strategy for locking such labile porphyrinoids that involved bis‐palladium coordination, a strategy [12] that has served as a robust paradigm for the resolution of racemic expanded porphyrinoids [13] . While this method has allowed for the successful chiral separation of octaphyrin [11, 12a–d] and hexaphyrin, [12e–f] it is important to recognize that it has yet to be generalized to include other intrinsically labile stereo‐structures [14] . On the other hand it is important to note that Latos‐Grażyński and co‐workers elegantly exploited phenanthrene to create polyaromatic hydrocarbon (PAH) embedded expanded carbaporphyrinoids.…”

Section: Introductionmentioning

confidence: 99%

Di‐2,7‐pyrenidecaphyrin(1.1.0.0.0.1.1.0.0.0) and Its Bis‐Organopalladium Complexes: Synthesis and Chiroptical Properties

et al. 2022

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A non-aromatic expanded carbaporphyrinoid, incorporating two built-in 2,7-pyrenylene moieties was synthesized. The intrinsically labile structure was demonstrated by proton-triggered conformational changes between the figure-of-eight and quasi-Möbius conformers. Upon treatment with Pd(OAc) 2 , the reaction produces two bis-Pd II complexes with distinct coordination modes. Metal coordination serves to fix the macrocyclic frameworks with the net result that both bis-Pd II complexes could be resolved by high performance liquid chromatography (HPLC) on a chiral stationary phase. The isolated enantiomers showed persistent chiroptical properties as evidenced by the intense response in the circular dichroism (CD) spectra and the record high absorption dissymmetry factors (g abs of up to 0.038) seen in the near-infrared spectral region. Moreover, the mutual interconversion of these two Pd II complexes was found to be stereospecific and to favor the more stable isomers under weakly acidic conditions.

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Bis-palladium(II) complex of doubly N-confused octaphyrin(1.1.1.1.1.1.1.1): Möbius aromaticity and chiroptical properties

Cited by 11 publications

References 50 publications

Resolution of Expanded Porphyrinoids: A Path to Persistent Chirality and Appealing Chiroptical Properties

Resolution of Expanded Porphyrinoids: A Path to Persistent Chirality and Appealing Chiroptical Properties

Creation from Confusion and Fusion in the Porphyrin World─The Last Three Decades of N-Confused Porphyrinoid Chemistry

Di‐2,7‐pyrenidecaphyrin(1.1.0.0.0.1.1.0.0.0) and Its Bis‐Organopalladium Complexes: Synthesis and Chiroptical Properties

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