Complexation of ferrocene derivatives by the cucurbit[7]uril host: A comparative study of the cucurbituril and cyclodextrin host families

Woo Sung Jeon, Kwangyul Moon, Sang Hyun Park, Hyungpil Chun, Young Ho Ko, Jin Yong Lee, Eun Sung Lee, S. Samal, N. Selvapalam, Mikhail V. Rekharsky, Vladimir Sindelar, David Sobransingh, Yoshihisa Inoue, Angel Kaifer, Kimoon Kim

Research output: Contribution to journalArticle

345 Citations (Scopus)

Abstract

The formation of inclusion complexes between cucurbit[7]uril (CB[7]) and ferrocene and its derivatives has been investigated. The X-ray crystal structure of the 1:1 inclusion complex between ferrocene and CB[7] revealed that the guest molecule resides in the host cavity with two different orientations. Inclusion of a set of five water-soluble ferrocene derivatives in CB[7] was investigated by 1H NMR spectroscopy and calorimetric and voltammetric techniques. Our data indicate that all neutral and cationic guests form highly stable inclusion complexes with CB[7], with binding constants in the 10 9-1010 M-1 and 1012-1013 M-1 ranges, respectively. However, the anionic ferrocenecarboxylate, the only negatively charged guest among those surveyed, was not bound by CB[7] at all. These results are in sharp contrast to the known binding behavior of the same guests to β-cyclodextrin (β-CD), since all the guests form stable inclusion complexes with β-CD, with binding constants in the range 103-104 M-1. The electrostatic surface potentials of CB[6], CB[7], and CB[8] and their size-equivalent CDs were calculated and compared. The CD portals and cavities exhibit low surface potential values, whereas the regions around the carbonyl oxygens in CBs are significantly negative, which explains the strong affinity of CBs for positively charged guests and also provides a rationalization for the rejection of anionic guests. Taken together, our data suggest that cucurbiturils may form very stable complexes. However, the host-guest interactions are very sensitive to some structural features, such as a negatively charged carboxylate group attached to the ferrocene residue, which may completely disrupt the stability of the complexes.

Original languageEnglish
Pages (from-to)12984-12989
Number of pages6
JournalJournal of the American Chemical Society
Volume127
Issue number37
DOIs
StatePublished - Sep 21 2005

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Cyclodextrins
Complexation
Derivatives
Surface potential
Nuclear magnetic resonance spectroscopy
Electrostatics
Static Electricity
Crystal structure
cucurbituril
ferrocene
cucurbit(7)uril
Magnetic Resonance Spectroscopy
X rays
X-Rays
Molecules
Oxygen
Water

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Complexation of ferrocene derivatives by the cucurbit[7]uril host : A comparative study of the cucurbituril and cyclodextrin host families. / Jeon, Woo Sung; Moon, Kwangyul; Park, Sang Hyun; Chun, Hyungpil; Ko, Young Ho; Lee, Jin Yong; Lee, Eun Sung; Samal, S.; Selvapalam, N.; Rekharsky, Mikhail V.; Sindelar, Vladimir; Sobransingh, David; Inoue, Yoshihisa; Kaifer, Angel; Kim, Kimoon.

In: Journal of the American Chemical Society, Vol. 127, No. 37, 21.09.2005, p. 12984-12989.

Research output: Contribution to journalArticle

Jeon, WS, Moon, K, Park, SH, Chun, H, Ko, YH, Lee, JY, Lee, ES, Samal, S, Selvapalam, N, Rekharsky, MV, Sindelar, V, Sobransingh, D, Inoue, Y, Kaifer, A & Kim, K 2005, 'Complexation of ferrocene derivatives by the cucurbit[7]uril host: A comparative study of the cucurbituril and cyclodextrin host families', Journal of the American Chemical Society, vol. 127, no. 37, pp. 12984-12989. https://doi.org/10.1021/ja052912c
Jeon, Woo Sung ; Moon, Kwangyul ; Park, Sang Hyun ; Chun, Hyungpil ; Ko, Young Ho ; Lee, Jin Yong ; Lee, Eun Sung ; Samal, S. ; Selvapalam, N. ; Rekharsky, Mikhail V. ; Sindelar, Vladimir ; Sobransingh, David ; Inoue, Yoshihisa ; Kaifer, Angel ; Kim, Kimoon. / Complexation of ferrocene derivatives by the cucurbit[7]uril host : A comparative study of the cucurbituril and cyclodextrin host families. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 37. pp. 12984-12989.
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abstract = "The formation of inclusion complexes between cucurbit[7]uril (CB[7]) and ferrocene and its derivatives has been investigated. The X-ray crystal structure of the 1:1 inclusion complex between ferrocene and CB[7] revealed that the guest molecule resides in the host cavity with two different orientations. Inclusion of a set of five water-soluble ferrocene derivatives in CB[7] was investigated by 1H NMR spectroscopy and calorimetric and voltammetric techniques. Our data indicate that all neutral and cationic guests form highly stable inclusion complexes with CB[7], with binding constants in the 10 9-1010 M-1 and 1012-1013 M-1 ranges, respectively. However, the anionic ferrocenecarboxylate, the only negatively charged guest among those surveyed, was not bound by CB[7] at all. These results are in sharp contrast to the known binding behavior of the same guests to β-cyclodextrin (β-CD), since all the guests form stable inclusion complexes with β-CD, with binding constants in the range 103-104 M-1. The electrostatic surface potentials of CB[6], CB[7], and CB[8] and their size-equivalent CDs were calculated and compared. The CD portals and cavities exhibit low surface potential values, whereas the regions around the carbonyl oxygens in CBs are significantly negative, which explains the strong affinity of CBs for positively charged guests and also provides a rationalization for the rejection of anionic guests. Taken together, our data suggest that cucurbiturils may form very stable complexes. However, the host-guest interactions are very sensitive to some structural features, such as a negatively charged carboxylate group attached to the ferrocene residue, which may completely disrupt the stability of the complexes.",
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AU - Ko, Young Ho

AU - Lee, Jin Yong

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AU - Sindelar, Vladimir

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AU - Kim, Kimoon

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N2 - The formation of inclusion complexes between cucurbit[7]uril (CB[7]) and ferrocene and its derivatives has been investigated. The X-ray crystal structure of the 1:1 inclusion complex between ferrocene and CB[7] revealed that the guest molecule resides in the host cavity with two different orientations. Inclusion of a set of five water-soluble ferrocene derivatives in CB[7] was investigated by 1H NMR spectroscopy and calorimetric and voltammetric techniques. Our data indicate that all neutral and cationic guests form highly stable inclusion complexes with CB[7], with binding constants in the 10 9-1010 M-1 and 1012-1013 M-1 ranges, respectively. However, the anionic ferrocenecarboxylate, the only negatively charged guest among those surveyed, was not bound by CB[7] at all. These results are in sharp contrast to the known binding behavior of the same guests to β-cyclodextrin (β-CD), since all the guests form stable inclusion complexes with β-CD, with binding constants in the range 103-104 M-1. The electrostatic surface potentials of CB[6], CB[7], and CB[8] and their size-equivalent CDs were calculated and compared. The CD portals and cavities exhibit low surface potential values, whereas the regions around the carbonyl oxygens in CBs are significantly negative, which explains the strong affinity of CBs for positively charged guests and also provides a rationalization for the rejection of anionic guests. Taken together, our data suggest that cucurbiturils may form very stable complexes. However, the host-guest interactions are very sensitive to some structural features, such as a negatively charged carboxylate group attached to the ferrocene residue, which may completely disrupt the stability of the complexes.

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