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 language | English |
|---|---|
| Journal | Journal of Porphyrins and Phthalocyanines |
| DOIs | |
| Publication status | Accepted/In press - Jan 1 2019 |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
Cite this
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.
In: Journal of Porphyrins and Phthalocyanines, 01.01.2019.Research output: Contribution to journal › Article
}
TY - JOUR
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.
UR - http://www.scopus.com/inward/record.url?scp=85072245695&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85072245695&partnerID=8YFLogxK
U2 - 10.1142/S1088424619501116
DO - 10.1142/S1088424619501116
M3 - Article
AN - SCOPUS:85072245695
JO - Journal of Porphyrins and Phthalocyanines
JF - Journal of Porphyrins and Phthalocyanines
SN - 1088-4246
ER -