Photoresponsive crown ethers. Part 14. Photoregulated crown-metal complexation by competitive intramolecular tail(ammonium)-biting

Seiji Shinkai, Midori Ishihara, Kaori Ueda, Osamu Manabe

Research output: Contribution to journalArticlepeer-review

66 Citations (Scopus)

Abstract

New photoresponsive crown ethers (1H+) having a crown ether ring and an ammoniumalkyl [H3N+-(CH2)n, n = 4,6,10] group attached to the two sides of an azobenzene have been synthesized. These photoresponsive 'tail-biting' crown ethers have been designed so that intramolecular 'biting' of the ammonium group to the crown can only occur upon photoisomerisation to the cis-forms. In the thermal cis-trans isomerisation, the first-order rate constants for cis- (1H+) were smaller by 1.6-2.2-fold than those for (1) (the analogous free amines). Moreover, this rate increased with increasing added K+ concentration. This suggests that the ammonium tail is intramolecularly bound to the crown ether ring in cis-(1H+). This intramolecular 'biting' is further reflected in the relative affinities of (1H+) for alkali-metal cations. The affinities were markedly reduced by u.v.-light irradiation and in particular, cis- (1H+) (n = 6) and cis-(1H+)(n = 10) showed almost no metal-binding ability. This marked difference in the metal-binding ability was used to generate the light-controlled systems for the passive or active ion-transport of ions across a liquid membrane.

Original languageEnglish
Pages (from-to)511-518
Number of pages8
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number4
DOIs
Publication statusPublished - Jan 1 1985
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Photoresponsive crown ethers. Part 14. Photoregulated crown-metal complexation by competitive intramolecular tail(ammonium)-biting'. Together they form a unique fingerprint.

Cite this