Complexation of ferrocene derivatives by the cucurbit[7]uril host: a comparative study of the cucurbituril and cyclodextrin host families.
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)-10(10) M(-)(1) and 10(12)-10(13) 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 beta-cyclodextrin (beta-CD), since all the guests form stable inclusion complexes with beta-CD, with binding constants in the range 10(3)-10(4) 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.
Jeon
Woo Sung
WS
Center for Supramolecular Science and Department of Chemistry, University of Miami, Coral Gables, Florida 33124-0431, USA.
Moon
Kwangyul
K
Park
Sang Hyun
SH
Chun
Hyungpil
H
Ko
Young Ho
YH
Lee
Jin Yong
JY
Lee
Eun Sung
ES
Samal
S
S
Selvapalam
N
N
Rekharsky
Mikhail V
MV
Sindelar
Vladimir
V
Sobransingh
David
D
Inoue
Yoshihisa
Y
Kaifer
Angel E
AE
Kim
Kimoon
K
D001952:Bridged-Ring Compounds / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003505:Cyclodextrins / Q000737:chemistry*; D005296:Ferrous Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D007093:Imidazoles / Q000737:chemistry*; D000075163:Metallocenes; D008958:Models, Molecular; D015394:Molecular Structure; D013816:Thermodynamics; D047028:Macrocyclic Compounds; D000099246:Cucurbit(n)urils
D001952:Bridged-Ring Compounds; D003505:Cyclodextrins; D005296:Ferrous Compounds; D007093:Imidazoles; D000075163:Metallocenes; C456276:cucurbit(7)uril; D047028:Macrocyclic Compounds; D000099246:Cucurbit(n)urils; C004998:ferrocene