Clathrates

Clathrates solid state host-guest compounds, consisting of a network of self-associating molecules forming cavities or charmels in which guest species can reside. They are usually only stable in the presence of guest species. 

The most common, and well-studied, clathrate systems are those in which water forms the host network, the clathrate hydrates. These are naturally occurring materials and are also of industrial importance and will be discussed separately in Section 4.4. First, we will look at a few representative examples of synthetic, organic clathrates that are created from a wide variety of molecules, each producing a unique network into which guests are included. 

Commensurate Structures Channel inclusion compounds in which there is a direct relationship between the repeat unit of the host structure and that of the guest. If no such simple relationship exists the structure is non-commensurate. 

The most interesting clathrate structures that form using TMA are those that involve one molecule of water per acid as a co-agent in the host 

Hydroquinone (4,2) exists in multiple forms in the solid state (a, (3 and y) but only p-hydroquinone is observed to form clathrates. The general formula for 

A Practical Guide to Supramolecular Chemistry Peter J. Cragg 2005 John Wiley Sons, Ltd ISBN 0-470-86653-5 

---

For physical processes, two examples are the elimination of normal paraffins from a mixture by their adsorption on 5 A molecular sieves or by their selective formation of solids with urea (clathrates)... 

Hydrates are solid structures composed of water molecules joined as crystals that have a system of cavities. The structure is stable only if at least one part of the cavities contains molecules of small molecular size. These molecules interact weakly with water molecules. Hydrates are not chemical compounds rather, they are clathrates . 

Diederich F, Jonas U, Gramlich V, Herrmann A, Ringsdorf H and Thilgen C 1993 Synthesis of a fullerene derivative of benzo[18]crown-6 by Diels-Alder reaction complexation ability, amphiphilic properties, and x-ray crystal structure of a dimethoxy-1,9-(methano[1, 2]benzomethano)fullerene[60] benzene clathrate Helv. Chim. Acta 76 2445-53... 

Krypton clathrates have been prepared with hydroquinone and phenol. 85Kr has found recent application in chemical analysis. By imbedding the isotope in various solids, kryptonates are formed. The activity of these kryptonates is sensitive to chemical reactions at the surface. Estimates of the concentration of reactants are therefore made possible. Krypton is used in certain photographic flash lamps for high-speed photography. Uses thus far have been limited because of its high cost. Krypton gas presently costs about 30/1. 

On the average, one part of radon is present ot 1 x IO21 part of air. At ordinary temperatures radon is a colorless gas when cooled below the freezing point, radon exhibits a brilliant phosphorescence which becomes yellow as the temperature is lowered and orange-red at the temperature of liquid air. It has been reported that fluorine reacts with radon, forming a fluoride. Radon clathrates have also been reported. 

Clathrate (Section 2 5) A mixture of two substances in which molecules of the minor component are held by van der Waals forces within a framework of molecules of the major component... 

Fig. 26. Clathrate receptor chemistry (a) a chiroselective crystalline host compound (clathrand) (b) a typical guest molecule to be included in the specified configuration and (c) the crystal stmcture of the respective clathrate (A and B denote host and C the guest species) (169).

J. Rebek, Jr., iu E. Weber, ed.. Molecular Inclusion and Molecular Recognition—Clathrates II, Top. Curr. Chem. Vol. 149, Springer, Bedia-Heidelberg, 1988, p. 189. 

Urea has the remarkable property of forming crystalline complexes or adducts with straight-chain organic compounds. These crystalline complexes consist of a hoUow channel, formed by the crystallized urea molecules, in which the hydrocarbon is completely occluded. Such compounds are known as clathrates. The type of hydrocarbon occluded, on the basis of its chain length, is determined by the temperature at which the clathrate is formed. This property of urea clathrates is widely used in the petroleum-refining industry for the production of jet aviation fuels (see Aviation and other gas-TURBINE fuels) and for dewaxing of lubricant oils (see also Petroleum, refinery processes). The clathrates are broken down by simply dissolving urea in water or in alcohol. 

Werner complexes can be used to form clathrates with the Cg aromatic isomers (35—42). The aromatic compounds are released upon heating. Since the uptake and release characteristics of the four Cg aromatic isomers are each different, this method has been suggested as a means of separating the isomers. 

Inclusion compounds of the Cg aromatic compounds with tris((9-phenylenedioxy)cyclotriphosphazene have been used to separate the individual isomers (43—47). The Schardinger dextrins, such as alpha-cyclodextrin, beta-dextrin, and gamma-dextrin are used for clathration alpha-dextrin is particularly useful for recovering PX from a Cg aromatic mixture (48,49). PyromeUitic dianhydride (50) and beryllium oxybenzoate (51) also form complexes, and procedures for separations were developed. 

Fats contribute to the rheological properties in flowable and pastry foods. By combining with starches to form a clathrate, a product different from the native starch is formed, eg, shortening in baked goods. The highly developed shortness of pies baked in eadier times resulted from the use of high levels of lard. The use of less fat in pie cmsts is evident, ie, the cmsts are harder and readily become soggy. 

The history of iaclusion compounds (1,2) dates back to 1823 when Michael Faraday reported the preparation of the clathrate hydrate of chlorine. Other early observations iaclude the preparation of graphite iatercalates ia 1841, the P-hydroquiaone H2S clathrate ia 1849, the choleic acids ia 1885, the cyclodexthn iaclusion compounds ia 1891, and the Hofmann s clathrate ia 1897. Later milestones of the development of iaclusion compounds refer to the tri-(9-thymotide benzene iaclusion compound ia 1914, pheaol clathrates ia 1935, and urea adducts ia 1940. 

Fig. 2. Classification/nomenclature of host—guest type inclusion compounds, definitions and relations (/) coordinative interaction, (2) lattice barrier interaction, (J) monomolecular shielding interaction (I) coordination-type inclusion compound (inclusion complex), (II) lattice-type inclusion compound (multimolecular/extramolecular inclusion compound, clathrate), (III) cavitate-type inclusion compound (monomolecular/intramolecular inclusion...

Extramolecular Cavity Inclusions Lattice-Type Inclusion Compounds, Clathrates... 

Fig. 11. Clathrate hydrates (a) basic structural component (H4QO2Q pentagonal dodecahedron) (b) type I host stmcture (two face-sharing 14-hedra are...

---