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

Biju Basumatary, Koki Mitsuno, Masatoshi Ishida, Hiroyuki Furuta

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Abstract

A novel bis-palladium(II) complex of doubly N-confused octaphyrin (Pd2-2) adopting a Möbius-Twisted topological structure was synthesized and characterized. Due to the effective 36p-electronic delocalization over the Möbius-Twisted octaphyrin scaffold, characteristic Soret and Q-like absorption features were observed in the near-infrared (NIR) region. However, the complex Pd2-2 exhibited weak aromatic character attributed to the distinct cross-conjugated resonance contribution as inferred from the 1H NMR chemical shifts as well as theoretical assessments (e.g. nucleus-independent chemical shift (NICS)). Since the bis-palladium(II) complexation of doubly N-confused octaphyrin 2 imparted significant conformational stability, topologically chiral enantiomers of Pd2-2 were successfully separated as (P)-and (M)-Twisted forms. The resulting isomers revealed relatively large circular dichroism (CD) responses with an absorption anisotropy factor of gabs = 0.009 in the NIR region (λ= 823 nm). In addition, the cyclic voltammogram of Pd2-2 revealed redox-rich properties due to its large p-conjugated system.

Original languageEnglish
JournalJournal of Porphyrins and Phthalocyanines
DOIs
Publication statusAccepted/In press - Jan 1 2019

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Palladium
Chemical shift
Infrared radiation
Enantiomers
Complexation
Scaffolds
Isomers
Anisotropy
Nuclear magnetic resonance
Oxidation-Reduction

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

@article{ec76a54bf9d8478c98151b922b5be2cd,
title = "Bis-palladium(II) complex of doubly N-confused octaphyrin(1.1.1.1.1.1.1.1): M{\"o}bius aromaticity and chiroptical properties",
abstract = "A novel bis-palladium(II) complex of doubly N-confused octaphyrin (Pd2-2) adopting a M{\"o}bius-Twisted topological structure was synthesized and characterized. Due to the effective 36p-electronic delocalization over the M{\"o}bius-Twisted octaphyrin scaffold, characteristic Soret and Q-like absorption features were observed in the near-infrared (NIR) region. However, the complex Pd2-2 exhibited weak aromatic character attributed to the distinct cross-conjugated resonance contribution as inferred from the 1H NMR chemical shifts as well as theoretical assessments (e.g. nucleus-independent chemical shift (NICS)). Since the bis-palladium(II) complexation of doubly N-confused octaphyrin 2 imparted significant conformational stability, topologically chiral enantiomers of Pd2-2 were successfully separated as (P)-and (M)-Twisted forms. The resulting isomers revealed relatively large circular dichroism (CD) responses with an absorption anisotropy factor of gabs = 0.009 in the NIR region (λ= 823 nm). In addition, the cyclic voltammogram of Pd2-2 revealed redox-rich properties due to its large p-conjugated system.",
author = "Biju Basumatary and Koki Mitsuno and Masatoshi Ishida and Hiroyuki Furuta",
year = "2019",
month = "1",
day = "1",
doi = "10.1142/S1088424619501116",
language = "English",
journal = "Journal of Porphyrins and Phthalocyanines",
issn = "1088-4246",
publisher = "Society of Porphyrins and Phthalocyanines (SPP)",

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T1 - Bis-palladium(II) complex of doubly N-confused octaphyrin(1.1.1.1.1.1.1.1)

T2 - Möbius aromaticity and chiroptical properties

AU - Basumatary, Biju

AU - Mitsuno, Koki

AU - Ishida, Masatoshi

AU - Furuta, Hiroyuki

PY - 2019/1/1

Y1 - 2019/1/1

N2 - A novel bis-palladium(II) complex of doubly N-confused octaphyrin (Pd2-2) adopting a Möbius-Twisted topological structure was synthesized and characterized. Due to the effective 36p-electronic delocalization over the Möbius-Twisted octaphyrin scaffold, characteristic Soret and Q-like absorption features were observed in the near-infrared (NIR) region. However, the complex Pd2-2 exhibited weak aromatic character attributed to the distinct cross-conjugated resonance contribution as inferred from the 1H NMR chemical shifts as well as theoretical assessments (e.g. nucleus-independent chemical shift (NICS)). Since the bis-palladium(II) complexation of doubly N-confused octaphyrin 2 imparted significant conformational stability, topologically chiral enantiomers of Pd2-2 were successfully separated as (P)-and (M)-Twisted forms. The resulting isomers revealed relatively large circular dichroism (CD) responses with an absorption anisotropy factor of gabs = 0.009 in the NIR region (λ= 823 nm). In addition, the cyclic voltammogram of Pd2-2 revealed redox-rich properties due to its large p-conjugated system.

AB - A novel bis-palladium(II) complex of doubly N-confused octaphyrin (Pd2-2) adopting a Möbius-Twisted topological structure was synthesized and characterized. Due to the effective 36p-electronic delocalization over the Möbius-Twisted octaphyrin scaffold, characteristic Soret and Q-like absorption features were observed in the near-infrared (NIR) region. However, the complex Pd2-2 exhibited weak aromatic character attributed to the distinct cross-conjugated resonance contribution as inferred from the 1H NMR chemical shifts as well as theoretical assessments (e.g. nucleus-independent chemical shift (NICS)). Since the bis-palladium(II) complexation of doubly N-confused octaphyrin 2 imparted significant conformational stability, topologically chiral enantiomers of Pd2-2 were successfully separated as (P)-and (M)-Twisted forms. The resulting isomers revealed relatively large circular dichroism (CD) responses with an absorption anisotropy factor of gabs = 0.009 in the NIR region (λ= 823 nm). In addition, the cyclic voltammogram of Pd2-2 revealed redox-rich properties due to its large p-conjugated system.

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