Cyclotriveratrylene inclusion complexes

Ibragimov, B. T., Makhkamov, K. K., Beketov, K. M., Polymorphism of crystalline inclusion complexes and unsolvated hosts. Part 8. Endocyclic modification of the cyclotriveratrylene host-guest complex with acetone. J. Incl. Phenom. Macro-... 

Similarly, cyclotriveratrylene forms an inclusion complex only with Cao, but not with Cvo- Again, the driving force is the creation of K-n charge transfer interactions. The X-ray structure is simplified in Figure 10 and shows that Ceo adopts a nesting position above the concave surface of cyclotriveratrylene, with close contacts between the two entities at the van der Waals limits (3.34 - 3.51 A). These short contacts compare well with the contacts in cubic close packed Ceo-... 

Matsubara, H. et al. Supramolecular inclusion complexes of fullerenes using cyclotriveratrylene derivatives with aromatic pendants. Chem. Lett. 27, 923-924,1998. 

An interesting example of the interplay between solid-state clathrands and solution-phase cavitands is provided by cyclotriveratrylene (CTV, 8). In the solid state, the saucer-shaped CTV molecules stack one on top of another in the two most common phases (x and and hence, while the molecules possess shallow molecular cavities, they do not include guests such as solvent molecules, which instead are located in voids between host stacks. However, larger guests such as buckminsterfuller-ene C6o, organometallic sandwich compounds,or carboranes form intracavity inclusion compounds, and the association persists in the solid state, with potential applications, for example, in the selective purification of fullerenes. Thus, CTV is both a cavitand and a clathrand. The cavitand behavior of CTV is highlighted by the chemistry of the double-CTV cryptophanes that form very stable solution complexes with a variety of halocarbon guests. 

The number of papers reporting the role of CH/ti interaction is rapidly increasing. Only recent key papers are cited here. Chloroform interacts favorably with an arene n-oloud of fullerene complexes of calixarenes " and cyclotriveratrylene. Evidence for the role of CH/ti interaction in self-assembly was presented.The significance in molecular capsules " " and lattice- and cavity-inclusion type clathrates is well documented. 

Cyclotriveratrylene is a trimeric, bowl-shaped molecular skeleton, known to form solid-state inclusion compounds. A variety of cyclotriveratrylene derivatives, e.g. 96 and 97, resulted from r-complexation of the aromatic nuclei with one, two, or three Ru( / -arene) (arene = CeHe, p-MeC6H4Pr ) and Ir( -C5Me5) organometallic moieties [195-197], Some of their structures were established by X-ray diffraction. 

As a natural development of the successful molecular inclusion concept, which involved electrostatic as well as van der Waals forces between the interacting host and guest entities, an increasing interest has been shown in the systematic study of lattice-inclusion type systems. A considerable effort has been devoted to the design of new hosts for the formation of stable crystaUine clathrates and the improvement of selective complexations with potential guests. Suitable examples of clathrates studied in recent years include hosts such as Dianin s compounds , perhydrotriphenylene , cyclotriveratrylene triphenylmethane hexakis-(arylthio) and -(arylthiomethyl)benzenes tri-o-thymotide (TOT) and choleic acids (cf. Fig. 1 in Ch. 1 of Vol. 140). Selected series of such clathrate inclusion systems have particularly been useful in research of photochemical reactions in the solid state and of selective molecular complexation that is central to biological phenomena... 

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