Clathrate different

Clathrates differ from zeolites in that the host structures are not usually stable in the absence of the guest. An exception is Dianin s compound (a chroman) where the porous hydrogen-bonded framework persists with no guest molecules to stabilise it. This is also true of a, B- and y- cyclodextrins, where the individual host molecules are like truncated sections of a hollow, gently tapering cone. 

Some data on the phases, forming in these systems, have been obtained (Table III). The difference in the pressures of the evolving gas for the DTA method(a sealed ampoule) and TG-analysis (a labyrinth sample holder) accounts for the difference in the decomposition temperatures for [NiBi X2] and [NiB X2] B. X-Ray powder diffractograms showed that Ni- and Co-clath-rates are isostructural and differ from Zn and Cd-clathrates, differing from each other. 

The unsaturat structures 41 and 42 provide a third possibility of arranging functional sensor ups at the same roof-sha] d skeleton in a gi n geometry. Here the sensors project in a perpendicular position with respect to the top ridge of the molecule instead of being inclined to one (cf. 37, 38) or both sides (cf. 26) of the roof. In 41, the carboxylic groups may interact intramolecularily, comparable to 38. Consequently 41 and 38 display rather similar (and poor) inclusion properties (Table 5), with one important difference however unlike 38,41 allows the formation of an inclusion comimund with t-butanol and, in addition, the stoichiometric ratios of the respective dioxane clathrates differ (1 1 in case of 41, but 2 1 for 38). In contrast to saturated monocarboxylic add 37, the unsaturated analogue 42 fails completely in inclusion formation... 

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. 

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. 

Molecular as well as ionic substances can form hydrates, but of an entirely different nature. In these crystals, sometimes referred to as clathrates, a molecule (such as CFI4, CHCI3) is quite literally trapped in an ice-like cage of water molecules. Perhaps the best-known molecular hydrate is that of chlorine, which has the approximate composition Cl2- 7.3H20. This compound was discovered by the great... 

According to these authors all gas hydrates crystallize in either of two cubic structures (I and II) in which the hydrated molecules are situated in cavities formed by a framework of water molecules linked together by hydrogen bonds. The numbers and sizes of the cavities differ for the two structures, but in both the water molecules are tetrahedrally coordinated as in ordinary ice. Apparently gas hydrates are clathrate compounds. 

Let us consider a clathrate crystal consisting of a cage-forming substance Q and a number of encaged compounds ( solutes ) A, B,. . ., M. The substance Q has two forms a stable modification, which under given conditions may be either crystalline (a) or liquid (L), and a metastable modification (ft) enclosing cavities of different types 1,. . ., n which acts as host lattice ( solvent ) in the clathrate. The number of cavities of type i per molecule of Q is denoted by vt. For hydroquinone v — for gas hydrates of Structure I 1/23 and v2 = 3/23, for those of Structure II vx = 2/17 and v2 = 1/17. 

Equation 13 has an important implication a clathrate behaves as an ideally dilute solution insofar as the chemical potential of the solvent is independent of the nature of the solutes and is uniquely determined by the total solute concentrations 2K yK1.. . 2x yKn in the different types of cavities. For a clathrate with one type of cavity the reverse is also true for a given value of fjiq (e.g. given concentration of Q in a liquid solution from which the clathrate is being crystallized) the fraction of cavities occupied 2kVk s uniquely determined by Eq. 13. When there are several types of cavities, however, this is no longer so since the individual occupation numbers 2k2/ki . ..,2k yKn, and hence the total solute concentration... 

There is one other three-phase equilibrium involving clathrates which is of considerable practical importance, namely that between a solution of Q, the clathrate, and gaseous A. For this equilibrium the previous formulas and many of the following conclusions also hold when replacing fiQa by fiQL, the chemical potential of Q in the liquid phase. But a complication then arises since yqL and the difference are not only... 

One important difference between the present and the previous case should be noted. For the hydroquinone clathrates, where the wall of a cavity consists of 12 OH groups, 6 adjacent carbon atoms, and 6 CH groups in ortho position to the OH groups, it seemed best to consider the product z qjk) as one unknown. For hydrates one may not do this the walls of both types of cavities consist exclusively of tetrahedrally-coordinated water molecules. Hence, one should use the same value of (,eg/k) —characteristic for a water molecule in a hydrate lattice—for both types of cavities and multi-... 

Along the three-phase line liquid-clathrate-gas the variation of the composition with temperature is considerable (cf. CD in Fig. 3), because when applying Eq. 27 to this equilibrium, the relatively small quantity AH = 0.16 kcal/mole has to be replaced by the much larger difference/ —//ql between the partial molar heat functions of / -hydroquinone and the liquid phase, which amounts to about —6 kcal/mole. The argon content of the solid reaches a minimum at the quadruple point. 

In the P-T projection the difference in slopes of the three-phase lines -clathrate-gas and liquid-clathrate-gas at the quadruple point R is determined by the heat of fusion of the number of moles of hydroquinone associated with one mole of argon in the clathrate under the conditions prevailing at R. If we extrapolate the three-phase line liquid-clathrate-gas to lower pressures (where it is no longer stable), the value of yA decreases until it becomes zero when we are dealing with pure / -hydroquinone. Hence, the metastable part of this three-phase line ends in the triple point B of /1-hydro-... 

Clathrate structures have been recently obtained also for s-PS [8] and s-PPMS [10]. In particular for s-PS, the treatment of amorphous samples, as well as of crystalline samples in the a or in the y form, produces clathrate structures including helices having s (2/1)2 symmetries, which present similar diffraction patterns, independently of the considered solvent. The treatment of samples of s-PPMS with suitable solvents also produces clathrate structures including s(2/l)2 helices however, the large differences in the X-ray diffraction patterns suggest different modes of packing, depending on the included solvent. 

However, the starch solution should not be omitted completely since the color difference between the chromatogram zones, in which the iodine is reduced to colorless iodide according to the iodine azide reaction mentioned above, and the background colored brown by unreacted iodine is considerably less than the difference in color between the deep blue background provided by the starch-iodine clathrate complex and the pale chromatogram zones. 

Several quantum-chemical studies have been performed on Hg(CN)2 and related species, applying different approaches with consideration of relativistic effects in order to get MO schemes and energies as a basis for discussion of bonding, valence XPS,105 UPS,106 XANES and EXAFS spectra.41 The latter study also showed Hg(CN)2 to be dissolved in H20 in molecular form (/-(Hg—C) 202, r(C—N) 114 pm), and obviously not to be hydrated, a remarkable finding insofar as solvates of Hg(CN)2 with various donor molecules are well known.2 However, in contrast to Cd(CN)2 (see above), Hg(CN)2 as such does not form clathrates. 

An enormous variety of solvates associated with many different kinds of compounds is reported in the literature. In most cases this aspect of the structure deserved little attention as it had no effect on other properties of the compound under investigation. Suitable examples include a dihydrate of a diphosphabieyclo[3.3.1]nonane derivative 29), benzene and chloroform solvates of crown ether complexes with alkyl-ammonium ions 30 54>, and acetonitrile (Fig. 4) and toluene (Fig. 5) solvates of organo-metallic derivatives of cyclotetraphosphazene 31. In most of these structures the solvent entities are rather loosely held in the lattice (as is reflected in relatively high thermal parameters of the corresponding atoms), and are classified as solvent of crystallization or a space filler 31a). However, if the geometric definition set at the outset is used to describe clathrates as crystalline solids in which guest molecules... 

The detailed structures of several clathrates have been characterized, and a certain degree of selectivity on complexation with different isomers has been detected 21). Most of these complexes are of the channel type, but some of them have structures which simultaneously qualify for channel and cage type descriptors representative examples are illustrated in Figs. 19-21. The crystal data of the complexes are summarized in Table 1. 

Additional observations reflect on the high stability of the DTU host lattice and illustrate its versatile capability to form clathrates with different guests. The crystalline 1 1 complexes of DTU with diethylether (Fig. 29) and diethylamine are isomorphous with the structure of the propanamide adduct (Fig. 24). However, in these structures the hydrogen bonds do not form a continuous pattern but are, rather, confined to... 

Selectivity studies with DTU indicated marked discrimination in the clathrate formation 23,45). As in other types of clathrates, the steric factor is important in differentiation between compounds of similar functionality but different shape. For example, DTU forms crystalline complexes with some alcohols (methanol, ethanol, propanol, 1-butanol) but not with others (2-butanol). It complexes the ethyl esters of N-acetyl derivatives of glycine, alanine, methionine and aspartic acid, but not of proline, serine, phenylalanine and glutamic acid. 

The possibility to resolve the two enantiomers of 27a (or 26) by crystalline complexa-tion with optically active 26 (or 27a) is mainly due to differences in topological complementarity between the H-bonded chains of host and guest molecules. In this respect, the spatial relationships which affect optical resolution in the above described coordination-assisted clathrates are similar to those characterizing some optically resolved molecular complexes S4). This should encourage additional applications of the lattice inclusion phenomena to problems of chiral recognition. 

Fig. 6. Diagrammatic (two-dimensional) representation of different modes of lattice inclusions involving coordinative (H-bond) interactions (indicated by broken lines) (a) cross-linked matrix type of inclusion (host-host interaction, true clathrate) (b) coordinatoclathrate type of inclusion (coordinative host-guest interaction, coordination-assisted clathrate)...

To probe the range of application of the new inclusion strategy (coordination-assisted clathrate formation) in different ways, directed structural modifications were undertaken starting from the basic constitution 1, for instance as to the molecular skeleton (basic structure) and/or the sensor section (functional groups). The formulae 7-24 show different possibilities of such variations. 

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