Photoresponsive crown ethers. Part 7. Proton and metal ion catalyses in the cis-trans isomerisation of azopyridines and an azopyridine-bridged cryptand

Seiji Shinkai, Takeshi Kouno, Yumiko Kusano, Osamu Manabe

Research output: Contribution to journalArticle

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Abstract

A 2,2′-azopyridine-bridged crown ether (5) has been synthesised for the purpose of controlling the ion-binding functions by an on-off light switch mechanism. Since the trans-azopyridine moiety of compound (5) [i.e. trans-(5)] is vertically over the crown ether ring and the photoisomerised cis-azopyridine moiety of (5) [i.e. cis-(5)] is almost parallel to the crown ether plane, it would be expected that only the pyridine nitrogens of trans-(5) are capable of co-ordinating to metal ions bound into the crown ether ring. The thermal isomerisation of cis-2,2′-azopyridine [cis-(3)] to trans-2,2′- azopyridine [trans-(3)] was speeded up either by protonation of the pyridine nitrogen or by complexation with heavy-metal ions (e.g. Cu2+, Ni 2+, and Co2+). Similarly, the thermal isomerisation of cis-(5) to trans-(5) was speeded up by protonation of the azopyridine, but the metal ion catalysis was observed only for the metal ions which were bound into the crown ether ring (e.g. Cu2+ and Pb2+). The result of solvent extraction of alkali-metal ions with (5) was very similar to that with an azobenzene-bridged crown ether (1), indicating that the 2,2′- azopyridine-bridge of (5) has almost no effect on the extraction of alkali-metal ions. On the other hand, trans-(5) was capable of extracting considerable amounts of heavy-metal ions (Cu2+, Ni2+, Co2+, and Hg2+), whereas photoisomerised cis-(5) scarcely extracted these metal ions. Such a difference in the extractability was not observed between trans-(1) and photoisomerised cis-(1). Neither the trans- nor the cis-form of 6,6′-bis(morpholinocarbonyl)-2,2′-azopyridine[non-crown analogue of (5)] could extract these metal ions under comparable extraction conditions. These results suggest that pyridine nitrogens of trans-(5) are directed towards the crown ether plane so as to co-ordinate to metal ions in the crown ether ring, whereas those of cis-(5) have no such co-ordination ability due to the distorted configuration. Therefore, compound (5) would act as a ' photoresponse cryptand ' for heavy metal ions.

Original languageEnglish
Pages (from-to)2741-2747
Number of pages7
JournalJournal of the Chemical Society, Perkin Transactions 1
Publication statusPublished - Dec 1 1982
Externally publishedYes

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Crown Ethers
Isomerization
Metal ions
Protons
Heavy Metals
Heavy ions
Alkali Metals
Nitrogen
Protonation
cryptand
Solvent extraction
Complexation
Catalysis

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Photoresponsive crown ethers. Part 7. Proton and metal ion catalyses in the cis-trans isomerisation of azopyridines and an azopyridine-bridged cryptand. / Shinkai, Seiji; Kouno, Takeshi; Kusano, Yumiko; Manabe, Osamu.

In: Journal of the Chemical Society, Perkin Transactions 1, 01.12.1982, p. 2741-2747.

Research output: Contribution to journalArticle

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abstract = "A 2,2′-azopyridine-bridged crown ether (5) has been synthesised for the purpose of controlling the ion-binding functions by an on-off light switch mechanism. Since the trans-azopyridine moiety of compound (5) [i.e. trans-(5)] is vertically over the crown ether ring and the photoisomerised cis-azopyridine moiety of (5) [i.e. cis-(5)] is almost parallel to the crown ether plane, it would be expected that only the pyridine nitrogens of trans-(5) are capable of co-ordinating to metal ions bound into the crown ether ring. The thermal isomerisation of cis-2,2′-azopyridine [cis-(3)] to trans-2,2′- azopyridine [trans-(3)] was speeded up either by protonation of the pyridine nitrogen or by complexation with heavy-metal ions (e.g. Cu2+, Ni 2+, and Co2+). Similarly, the thermal isomerisation of cis-(5) to trans-(5) was speeded up by protonation of the azopyridine, but the metal ion catalysis was observed only for the metal ions which were bound into the crown ether ring (e.g. Cu2+ and Pb2+). The result of solvent extraction of alkali-metal ions with (5) was very similar to that with an azobenzene-bridged crown ether (1), indicating that the 2,2′- azopyridine-bridge of (5) has almost no effect on the extraction of alkali-metal ions. On the other hand, trans-(5) was capable of extracting considerable amounts of heavy-metal ions (Cu2+, Ni2+, Co2+, and Hg2+), whereas photoisomerised cis-(5) scarcely extracted these metal ions. Such a difference in the extractability was not observed between trans-(1) and photoisomerised cis-(1). Neither the trans- nor the cis-form of 6,6′-bis(morpholinocarbonyl)-2,2′-azopyridine[non-crown analogue of (5)] could extract these metal ions under comparable extraction conditions. These results suggest that pyridine nitrogens of trans-(5) are directed towards the crown ether plane so as to co-ordinate to metal ions in the crown ether ring, whereas those of cis-(5) have no such co-ordination ability due to the distorted configuration. Therefore, compound (5) would act as a ' photoresponse cryptand ' for heavy metal ions.",
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T1 - Photoresponsive crown ethers. Part 7. Proton and metal ion catalyses in the cis-trans isomerisation of azopyridines and an azopyridine-bridged cryptand

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N2 - A 2,2′-azopyridine-bridged crown ether (5) has been synthesised for the purpose of controlling the ion-binding functions by an on-off light switch mechanism. Since the trans-azopyridine moiety of compound (5) [i.e. trans-(5)] is vertically over the crown ether ring and the photoisomerised cis-azopyridine moiety of (5) [i.e. cis-(5)] is almost parallel to the crown ether plane, it would be expected that only the pyridine nitrogens of trans-(5) are capable of co-ordinating to metal ions bound into the crown ether ring. The thermal isomerisation of cis-2,2′-azopyridine [cis-(3)] to trans-2,2′- azopyridine [trans-(3)] was speeded up either by protonation of the pyridine nitrogen or by complexation with heavy-metal ions (e.g. Cu2+, Ni 2+, and Co2+). Similarly, the thermal isomerisation of cis-(5) to trans-(5) was speeded up by protonation of the azopyridine, but the metal ion catalysis was observed only for the metal ions which were bound into the crown ether ring (e.g. Cu2+ and Pb2+). The result of solvent extraction of alkali-metal ions with (5) was very similar to that with an azobenzene-bridged crown ether (1), indicating that the 2,2′- azopyridine-bridge of (5) has almost no effect on the extraction of alkali-metal ions. On the other hand, trans-(5) was capable of extracting considerable amounts of heavy-metal ions (Cu2+, Ni2+, Co2+, and Hg2+), whereas photoisomerised cis-(5) scarcely extracted these metal ions. Such a difference in the extractability was not observed between trans-(1) and photoisomerised cis-(1). Neither the trans- nor the cis-form of 6,6′-bis(morpholinocarbonyl)-2,2′-azopyridine[non-crown analogue of (5)] could extract these metal ions under comparable extraction conditions. These results suggest that pyridine nitrogens of trans-(5) are directed towards the crown ether plane so as to co-ordinate to metal ions in the crown ether ring, whereas those of cis-(5) have no such co-ordination ability due to the distorted configuration. Therefore, compound (5) would act as a ' photoresponse cryptand ' for heavy metal ions.

AB - A 2,2′-azopyridine-bridged crown ether (5) has been synthesised for the purpose of controlling the ion-binding functions by an on-off light switch mechanism. Since the trans-azopyridine moiety of compound (5) [i.e. trans-(5)] is vertically over the crown ether ring and the photoisomerised cis-azopyridine moiety of (5) [i.e. cis-(5)] is almost parallel to the crown ether plane, it would be expected that only the pyridine nitrogens of trans-(5) are capable of co-ordinating to metal ions bound into the crown ether ring. The thermal isomerisation of cis-2,2′-azopyridine [cis-(3)] to trans-2,2′- azopyridine [trans-(3)] was speeded up either by protonation of the pyridine nitrogen or by complexation with heavy-metal ions (e.g. Cu2+, Ni 2+, and Co2+). Similarly, the thermal isomerisation of cis-(5) to trans-(5) was speeded up by protonation of the azopyridine, but the metal ion catalysis was observed only for the metal ions which were bound into the crown ether ring (e.g. Cu2+ and Pb2+). The result of solvent extraction of alkali-metal ions with (5) was very similar to that with an azobenzene-bridged crown ether (1), indicating that the 2,2′- azopyridine-bridge of (5) has almost no effect on the extraction of alkali-metal ions. On the other hand, trans-(5) was capable of extracting considerable amounts of heavy-metal ions (Cu2+, Ni2+, Co2+, and Hg2+), whereas photoisomerised cis-(5) scarcely extracted these metal ions. Such a difference in the extractability was not observed between trans-(1) and photoisomerised cis-(1). Neither the trans- nor the cis-form of 6,6′-bis(morpholinocarbonyl)-2,2′-azopyridine[non-crown analogue of (5)] could extract these metal ions under comparable extraction conditions. These results suggest that pyridine nitrogens of trans-(5) are directed towards the crown ether plane so as to co-ordinate to metal ions in the crown ether ring, whereas those of cis-(5) have no such co-ordination ability due to the distorted configuration. Therefore, compound (5) would act as a ' photoresponse cryptand ' for heavy metal ions.

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