In 1981, the macrocyclic methylene-bridged glycoluril hexamer (CB[6]) was dubbed "cucurbituril" by Mock and co-workers because of its resemblance to the most prominent member of the cucurbitaceae family of plants--the pumpkin. In the intervening years, the fundamental binding properties of CB[6]-high affinity, highly selective, and constrictive binding interactions--have been delineated by the pioneering work of the research groups of Mock, Kim, and Buschmann, and has led to their applications in waste-water remediation, as artificial enzymes, and as molecular switches. More recently, the cucurbit[n]uril family has grown to include homologues (CB[5]-CB[10]), derivatives, congeners, and analogues whose sizes span and exceed the range available with the alpha-, beta-, and gamma-cyclodextrins. Their shapes, solubility, and chemical functionality may now be tailored by synthetic chemistry to play a central role in molecular recognition, self-assembly, and nanotechnology. This Review focuses on the synthesis, recognition properties, and applications of these unique macrocycles.

The cucurbit[n]uril family

Fluorescent Dyes and Their Supramolecular Host/Guest Complexes with Macrocycles in Aqueous Solution Roy N. Dsouza, Uwe Pischel,* and Werner M. Nau* School of Engineering and Science, Jacobs University Bremen, Campus Ring 1, D-28759 Bremen, Germany Centro de Investigaci on en Química Sostenible (CIQSO) and Departamento de Ingeniería Química, Química Física y Química Org anica, Universidad de Huelva, Campus de El Carmen s/n, E-21071 Huelva, Spain

Fluorescent dyes and their supramolecular host/guest complexes with macrocycles in aqueous solution.

The factors affecting host-guest complexation between the molecular container compound cucurbit[6]uril (CB6) and various guests in aqueous solution are studied, and a detailed complexation mechanism in the presence of cations is derived. The formation of the supramolecular complex is studied in detail for cyclohexylmethylammonium ion as guest. The kinetics and thermodynamics of complexation is monitored by NMR as a function of temperature, salt concentration, and cation size. The binding constants and the ingression rate constants decrease with increasing salt concentration and cation-binding constant, in agreement with a competitive binding of the ammonium site of the guest and the metal cation with the ureido carbonyl portals of CB6. Studies as a function of guest size indicate that the effective container volume of the CB6 cavity is approximately 105 A(3). It is suggested that larger guests are excluded for two reasons: a high activation barrier for ingression imposed by the tight CB6 portals and a destabilization of the complex due to steric repulsion inside. For example, in the case of the nearly spherical azoalkane homologues 2,3-diazabicyclo[2.2.1]hept-2-ene (DBH, volume ca. 96 A(3)) and 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO, volume ca. 110 A(3)), the former forms the CB6 complex promptly with a sizable binding constant (1300 M(-1)), while the latter does not form a complex even after several months at optimized complexation conditions. Molecular mechanics calculations are performed for several CB6/guest complexes. A qualitative agreement is found between experimental and calculated activation energies for ingression as a function of both guest size and state of protonation. The potential role of constrictive binding by CB6 is discussed.

Mechanism of host-guest complexation by cucurbituril.

Im Jahre 1981 tauften Mock und Mitarbeiter das makrocyclische methylenverbruckte Glycoluril-Hexamer (CB[6]) auf den Namen “Cucurbituril” – da ihre Form einem Kurbis ahnelt, dem bekanntesten Mitglied der Cucurbitaceae-Familie in der Pflanzenwelt. In den folgenden Jahren wurden die grundlegenden Bindungseigenschaften von CB[6] – die hohe Affinitat und Selektivitat sowie der Einschluss von Gasten – in bahnbrechenden Arbeiten der Gruppen von Mock, Kim und Buschmann aufgezeigt; es folgten Anwendungen in der Wasseraufarbeitung, kunstlichen Enzymen und molekularen Schaltern. Erst vor kurzem wuchs die Cucurbit[n]uril-Familie um Homologe (CB[5]–CB[10]), Derivate, Verwandte und Analoga, sodass sie nun die Molekulgrosen von α-, β- und γ-Cyclodextrinen umfasst und ubersteigt. Auch die Formen, Loslichkeiten und chemischen Funktionalitaten konnen inzwischen durch spezielle Synthesen den Erfordernissen angepasst werden. Durch diese Eigenschaften sind die Cucurbiturile pradestiniert fur eine zentrale Rolle in molekularer Erkennung, Selbstorganisation und Nanotechnologie. Dieser Aufsatz stellt Synthesen, Erkennungseigenschaften und Anwendungen dieser einzigartigen Makrocyclen vor.

Die Cucurbit[n]uril-Familie

The photophysical properties of the phenazine-based dye neutral red were investigated in aqueous solution in the presence of the macrocyclic host molecule cucurbit[7]uril (CB7) using ground-state absorption as well as steady-state and time-resolved fluorescence measurements. The results are contrasted to those previously obtained for beta-cyclodextrin (beta-CD; Singh et al. J. Phys. Chem. A 2004, 108, 1465). Both the neutral (NR) and cationic (NRH+) forms of the dye formed inclusion complexes with CB7, with the larger binding constant for the latter (K = 6.5 x 10(3) M(-1) versus 6.0 x 10(5) M(-1)). This result differed from that for beta-CD, where only the neutral form of the dye was reported to undergo sizable inclusion complex formation. From the difference in binding constants and the pK(a) value of protonated neutral red in the absence of CB7 (6.8), an increased pK(a) value of the dye when complexed by CB7 was projected (approximately 8.8). This shift differed again from the behavior of the dye with beta-CD, where a decreased pK(a) value (ca. 6.1) was reported. The photophysical properties of both NR and NRH+ forms showed significant changes in the presence of CB7. Fluorescence anisotropy studies indicated that the inclusion complexes of both forms of the dye rotate as a whole, giving rotational relaxation times much larger than that expected for the free dye in aqueous solution. The thermodynamic parameters for the NRH+.CB7 complex were investigated in temperature-dependent binding studies, suggesting an entropic driving force for complexation related to desolvation of the cation and the removal of high-energy water molecules from the CB7 cavity.

Host-guest complexation of neutral red with macrocyclic host molecules: contrasting pK(a) shifts and binding affinities for cucurbit[7]uril and beta-cyclodextrin.

Fluorescence enhancement of a probe molecule in solution by the container molecule cucurbituril (CB) is reported for the first time. The fluorescence of the probe 2-anilinonaphthalene-6-sulfonate (...

A fluorescent host-guest complex of cucurbituril in solution: a molecular Jack O'Lantern

A solid precipitate is formed immediately upon the mixing of aqueous salt solutions of the fluorescence probe 1-anilino-8-naphthalenesulfonate (1,8-ANS) and the cage compound cucurbituril. The resu...

Andrew I. MacRae

Papers

A fluorescent host-guest complex of cucurbituril in solution: a molecular Jack O'Lantern

The Lattice Inclusion Compound of 1,8-ANS and Cucurbituril: A Unique Fluorescent Solid