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 language | English |
|---|---|
| Pages (from-to) | 12984-12989 |
| Number of pages | 6 |
| Journal | Journal of the American Chemical Society |
| Volume | 127 |
| Issue number | 37 |
| DOIs | |
| State | Published - Sep 21 2005 |
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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 journal › Article
}
TY - JOUR
T1 - Complexation of ferrocene derivatives by the cucurbit[7]uril host
T2 - A comparative study of the cucurbituril and cyclodextrin host families
AU - Jeon, Woo Sung
AU - Moon, Kwangyul
AU - Park, Sang Hyun
AU - Chun, Hyungpil
AU - Ko, Young Ho
AU - Lee, Jin Yong
AU - Lee, Eun Sung
AU - Samal, S.
AU - Selvapalam, N.
AU - Rekharsky, Mikhail V.
AU - Sindelar, Vladimir
AU - Sobransingh, David
AU - Inoue, Yoshihisa
AU - Kaifer, Angel
AU - Kim, Kimoon
PY - 2005/9/21
Y1 - 2005/9/21
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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=25144489591&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=25144489591&partnerID=8YFLogxK
U2 - 10.1021/ja052912c
DO - 10.1021/ja052912c
M3 - Article
C2 - 16159293
AN - SCOPUS:25144489591
VL - 127
SP - 12984
EP - 12989
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 37
ER -