Calixarene – A Versatile Host 

Calixarenes were developed later than crown ethers and cyclodextrins but have still been
extensively researched. Macrocycles of calix[n]arenes are constructed by linking a number of
phenol residues via methylene moieties (Fig. 2.16). Like crown ethers, the name “calixarene”
reflects the structures of these molecules, since a calix is a chalice. Calixarenes with various cavity
sizes have been designed, each of which has conformation isomers, and their phenolic hydroxyl
groups are often modified. These structural characteristics allow us to create calixarene derivatives
with various structural modifications. 
The conformational isomers of a calixarene with four phenol residues are shown in Fig. 2.17.
The isomers vary in terms of the orientations of their phenol groups: (a) has a cone structure with
all of the phenols pointing to the same direction; (b) has a partial cone structure with one phenol
pointing in a different direction to the others; (c) has a 1,3-alternate structure with neighboring
phenols pointing in opposite directions. These isomeric hosts have different selectivities for metal
ion inclusion in the upper cavity and the lower cavity. Of course, changing the number of phenol
residues alters the guest size appropriate for effective inclusion. 
Figure 2.16. Calix[n]arene
2.8 Calixarene – A Versatile Host 25 

The calix[8]arene depicted in Fig. 2.18 can bind fullerenes (see Chap. 3); the fullerene “soccer
ball” is trapped in the calix. Fullerenes are usually prepared as mixture of C 60, C70, C76, and so on,
and separating them is not always easy. The calix[8]arene has a cavity with an inner diameter of
∼1nm, which is therefore suitable for C 60, since it has a diameter of ∼0.7nm. When the calixarene is
added to a toluene solution of a mixture of fullerenes, a 1:1 complex of the calixarene and C 60
selectively precipitates. Isolation of the precipitates followed by dispersion of them in chloroform
results in the precipitation of dissociated C 60. Repeating these processes results in C 60 with high
purity. 
Since the phenolic hydroxyl groups can be modified in various ways, we can design an array of
functionalized hosts. Figure 2.19 shows the structure of calixcrown, in which two hydroxyl groups in
calix[4]arene are bridged by an oligoethylene glycol chain. The flexibility of the crown part is highly
restricted in this structure, resulting in highly selective molecular recognition. The size of this
binding site is quite close to the size of a sodium ion. The binding affinity of the calixcrown to a
sodium ion is 100 000 times greater than that observed for a potassium ion. 
Another interesting example involves a calixarene that exhibits a color change upon the binding
of a chiral guest. When converting the chiral recog nition phenomenon into a change of color, the
design of the host molecule attaching to the chromophore is critical. The host molecule shown in
Fig. 2.20 

Figure 2.17. Conformation isomers and ion binding behavior of calix[4]arene

26 2 The Chemistry of Molecular Recognition – Host Molecules and Guest Molecules Figure 2.18. Binding of
fullerene by calix[8]arene 
Figure 2.19. Calixcrown 

possesses two dye moieties and a chiral binaphthyl group. When a guest molecule (phenyl
glycinol) is added to the host (dissolved in ethanol), the solution color changes depending on the
chirality of the guest. The original color of the guest-free host is red; addition of R-phenyl glycinol
changes the color to blue-purple. In contrast, the solution color remains red upon the ad dition of S-
phenyl glycinol. When R-phenyl glycinol is bound to the host, the left-hand indophenol (dye A) in
the host is deprotonated and the right-hand indophenol (dye B) interacts more with the hydrophobic
environment of the binaphthyl group. These changes cause the complex to change color. In con-
2.8 Calixarene – A Versatile Host 27 Figure 2.20. Chiral recognition by a dye-carrying calixarene
28 2 The Chemistry of Molecular Recognition – Host Molecules and Guest Molecules 
trast, binding S-phenyl glycinol to the same host produces a complex with a different geometry,
especially in terms of the relative positions of the phenyl group and the binaphthyl group. The
spectral shift in dye B is suppressed and the color change is not so pronounced. In this system,
differences in the in teractions between the guest and the binaphthyl group lead to different color
changes depending upon the chirality of the guest.