Rapid metal ions shuttling through 1,3-alternate thiacalix[4]crown tubes

Jae Kwang Lee; Sung Kuk Kim; Richard A. Bartsch; Jacques Vicens; Sotaro Miyano; Jong Seung Kim

doi:10.1021/jo034666y

Rapid metal ions shuttling through 1,3-alternate thiacalix[4]crown tubes

Jae Kwang Lee, Sung Kuk Kim, Richard A. Bartsch, Jacques Vicens, Sotaro Miyano, Jong Seung Kim

Research output: Contribution to journal › Article › peer-review

45 Citations (Scopus)

Abstract

Several new thiacalix[4]monocrown and thiacalix[4]biscrown compounds were synthesized. Their metal ion extractabilities are found to be lower than those of conventional calix[4]crowns. By use of X-ray crystal structures and ¹H NMR spectroscopy, this result is explained by weaker electrostatic interactions of the polyether ring oxygen atoms with the metal ions and diminished π-metal ion interactions between the metal ions and the aromatic rings of the thiacalix[4]crowns. Temperature-dependent ¹H NMR spectroscopic measurements reveal coalescence temperatures T _c^intra and T_c^inter for metal ion exchange. In one case, this exchange was rationalized as metal ion shuttling through a thiacalix[4]biscrown tube. Since the metal ions are less tightly complexed by the polyether units in thiacalix[4]biscrowns than in conventional calix[4]biscrowns, more facile metal ion exchange between the two polyether units takes place in the former.

Original language	English
Pages (from-to)	6720-6725
Number of pages	6
Journal	Journal of Organic Chemistry
Volume	68
Issue number	17
DOIs	https://doi.org/10.1021/jo034666y
Publication status	Published - 2003 Sept 1
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry

Access to Document

10.1021/jo034666y

Cite this

@article{bbb2431a13824ff6a268cd10375a4a75,

title = "Rapid metal ions shuttling through 1,3-alternate thiacalix[4]crown tubes",

abstract = "Several new thiacalix[4]monocrown and thiacalix[4]biscrown compounds were synthesized. Their metal ion extractabilities are found to be lower than those of conventional calix[4]crowns. By use of X-ray crystal structures and 1H NMR spectroscopy, this result is explained by weaker electrostatic interactions of the polyether ring oxygen atoms with the metal ions and diminished π-metal ion interactions between the metal ions and the aromatic rings of the thiacalix[4]crowns. Temperature-dependent 1H NMR spectroscopic measurements reveal coalescence temperatures T cintra and Tcinter for metal ion exchange. In one case, this exchange was rationalized as metal ion shuttling through a thiacalix[4]biscrown tube. Since the metal ions are less tightly complexed by the polyether units in thiacalix[4]biscrowns than in conventional calix[4]biscrowns, more facile metal ion exchange between the two polyether units takes place in the former.",

author = "Lee, {Jae Kwang} and Kim, {Sung Kuk} and Bartsch, {Richard A.} and Jacques Vicens and Sotaro Miyano and Kim, {Jong Seung}",

year = "2003",

month = sep,

day = "1",

doi = "10.1021/jo034666y",

language = "English",

volume = "68",

pages = "6720--6725",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "17",

}

TY - JOUR

T1 - Rapid metal ions shuttling through 1,3-alternate thiacalix[4]crown tubes

AU - Lee, Jae Kwang

AU - Kim, Sung Kuk

AU - Bartsch, Richard A.

AU - Vicens, Jacques

AU - Miyano, Sotaro

AU - Kim, Jong Seung

PY - 2003/9/1

Y1 - 2003/9/1

N2 - Several new thiacalix[4]monocrown and thiacalix[4]biscrown compounds were synthesized. Their metal ion extractabilities are found to be lower than those of conventional calix[4]crowns. By use of X-ray crystal structures and 1H NMR spectroscopy, this result is explained by weaker electrostatic interactions of the polyether ring oxygen atoms with the metal ions and diminished π-metal ion interactions between the metal ions and the aromatic rings of the thiacalix[4]crowns. Temperature-dependent 1H NMR spectroscopic measurements reveal coalescence temperatures T cintra and Tcinter for metal ion exchange. In one case, this exchange was rationalized as metal ion shuttling through a thiacalix[4]biscrown tube. Since the metal ions are less tightly complexed by the polyether units in thiacalix[4]biscrowns than in conventional calix[4]biscrowns, more facile metal ion exchange between the two polyether units takes place in the former.

AB - Several new thiacalix[4]monocrown and thiacalix[4]biscrown compounds were synthesized. Their metal ion extractabilities are found to be lower than those of conventional calix[4]crowns. By use of X-ray crystal structures and 1H NMR spectroscopy, this result is explained by weaker electrostatic interactions of the polyether ring oxygen atoms with the metal ions and diminished π-metal ion interactions between the metal ions and the aromatic rings of the thiacalix[4]crowns. Temperature-dependent 1H NMR spectroscopic measurements reveal coalescence temperatures T cintra and Tcinter for metal ion exchange. In one case, this exchange was rationalized as metal ion shuttling through a thiacalix[4]biscrown tube. Since the metal ions are less tightly complexed by the polyether units in thiacalix[4]biscrowns than in conventional calix[4]biscrowns, more facile metal ion exchange between the two polyether units takes place in the former.

UR - http://www.scopus.com/inward/record.url?scp=0043010999&partnerID=8YFLogxK

U2 - 10.1021/jo034666y

DO - 10.1021/jo034666y

M3 - Article

C2 - 12919039

AN - SCOPUS:0043010999

SN - 0022-3263

VL - 68

SP - 6720

EP - 6725

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 17

ER -

Rapid metal ions shuttling through 1,3-alternate thiacalix[4]crown tubes

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this