Metal-mediated self-assembly of pyridylcalixarenes: Prevention of intramolecular metal chelation is essential in constructing molecular capsules

Z. Zhong, A. Ikeda, M. Ayabe, Seiji Shinkai, S. Sakamoto, K. Yamaguchi

Research output: Contribution to journalArticle

72 Citations (Scopus)

Abstract

To construct calixarene-based molecular capsules utilizing the pyridyl-Pd(II) interaction, reactions of cone-pyridylcalix[4]arene 3, cone-pyridylcalix[5]arene 13, and cone-pyridylcalix[4]arene bis-crown 16 with square-planar Pd(II) complex 7 were investigated. Because of the coexistence of intermolecular binding and chelate-forming intramolecular binding, the reactions of cone-pyridylcalix[4]arene 3 or cone-pyridylcalix[5]arene 13 with cis-Pd(II) complex 7 yield complicated, structure-unknown oligomers. The short dioxyethylene bridges on the lower rim of pyridylcalix-[4]arene bis-crown 16 rigidify the cone conformation and thus prohibit 16 from the intramolecular binding with a metal component. Thus, two cone-tetrapyridylcalix[4]arene bis-crown 16 and four cis-Pd(II) complex molecules self-assemble into molecular capsules that exist as a parallel/antiparallel conformer mixture in a nearly 1:1 ratio. The results demonstrated that to prevent entropically favorable intramolecular binding is essential in constructing higher capsule-like structures with calixarene building blocks by self-assembling.

Original languageEnglish
Pages (from-to)1002-1008
Number of pages7
JournalJournal of Organic Chemistry
Volume66
Issue number3
DOIs
Publication statusPublished - Feb 9 2001

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Chelation
Self assembly
Capsules
Cones
Metals
Calixarenes
Oligomers
Conformations
Molecules

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Metal-mediated self-assembly of pyridylcalixarenes : Prevention of intramolecular metal chelation is essential in constructing molecular capsules. / Zhong, Z.; Ikeda, A.; Ayabe, M.; Shinkai, Seiji; Sakamoto, S.; Yamaguchi, K.

In: Journal of Organic Chemistry, Vol. 66, No. 3, 09.02.2001, p. 1002-1008.

Research output: Contribution to journalArticle

Zhong, Z. ; Ikeda, A. ; Ayabe, M. ; Shinkai, Seiji ; Sakamoto, S. ; Yamaguchi, K. / Metal-mediated self-assembly of pyridylcalixarenes : Prevention of intramolecular metal chelation is essential in constructing molecular capsules. In: Journal of Organic Chemistry. 2001 ; Vol. 66, No. 3. pp. 1002-1008.
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