Graphite inclusion compounds intercalation

We shall be discussing other types of inclusion compounds formed by layered graphite and Ta 2 as well as other varieties of hosts in Chapter 8, which deals with intercalation chemistry. 

The history of inclusion compounds (1,2) dates back to 1823 when Michael Faraday reported the preparation of the clathrate hydrate of chlorine. Other early observations include the preparation of graphite intercalates in 1841, the 3-hydroquinone H2S clathrate in 1849, the choleic acids in 1885, the cyclodextrin inclusion compounds in 1891, and the Hofmann s clathrate in 1897. Later milestones of the development of inclusion compounds refer to the tri-o-thymotide benzene inclusion compound in 1914, phenol clathrates in 1935, and urea adducts in 1940. 

Sir Humphry Davy discovery of chlorine hydrate 1823 - Michael Faraday formula of chlorine hydrate 1841 - C. Schafhautl study of graphite intercalates 1849 - F. Wohler /Lquinol H2S clathrate 1891 - Villiers and Hebd cyclodextrin inclusion compounds... 

In principle, the negatively charged, presumably planar network I can be combined with one molar equivalent of tetraalkylammonium ion IGN"1" of the right size as interlayer template to yield a crystalline inclusion compound of stoichiometric formula (IGN+) I C(NIG ) ICO2 that is reminiscent of the graphite intercalates. Anionic network n, on the other hand, needs twice as many monovalent cations for charge balance, and furthermore possesses honeycomb-like host cavities of diameter 700 pm that must be filled by... 

The chemistry of inclusion compounds also looks back on a lively history There are many events of significance in the area of inclusion chemistry till the middle of the twentieth century including the discovery of new inclusion compounds and hosts (Fig. 1), among them the graphite intercalates, the P-quinol and cyclodextrin inclusion compounds, the Hofmann-type clathrates as well as the inclusion compounds of tri-o-thymotide, Dianin s compound, the choleic acids, of phenols, of urea and others specified in comprehensive monographs... 

Hofmann-type clathrates Werner clathrates clathrate hydrates inclusion compounds of urea, thiourea, and selenourea cyclodextrins calixarenes gossypol hexa-hosts hydroquinone phenol and Dianin s compounds graphite intercalates natural and pillared clays and others. Such studies contributed to the birth of supramolecular chemistry, with relevance to a new understanding of the world of materials that was emphasized with a Nobel Prize. 

The concept of inclusion is as old as humankind. The hand is capable of a variable assortment of inclusions, and many analogies are appropriate. The first verified examples of inclusion compounds date from the early 1800s. It is instructive to list the dates of record for the preparation of inclusion compounds of various types the chlorine clathrate hydrate by Faraday in 1823, graphite intercalates in 1841, the /3-quinol H2S clathrate in 1849,... 

At this time, no all-inclusive rule can be given that will predict whether a given compound will intercalate or not. Most of the information available seems to have been obtained empirically. Such analogies as similar chemical properties have been helpful. The many factors that infiuence the intercalation process have been surveyed by Herold (H14). In Tables II-VI are listed metal halides considered to intercalate into graphite, together with some structural information (S2J, i 9). Several general characteristics have been ascribed to intercalat-... 

The structure of the intercalates are of considerable interest, in that the intercalate material enters the graphite layers to form in the final analysis, a one-to-one graphite-intercalate layer structure. Intermediate compounds involve inclusion of the material in, for example, a second, fourth, or fifth layer rather than dilution of the amount in the same layer. The chemical bonding in the compounds appears to be ionic and certainly involves electron transfer probably, for example, from potassium to the upper pi-band of graphite. ... 

Intercalation constitutes an important case of inclusion phenomena in which the host lattice is characterized by a lamellar structure [39]. Graphite yields both anion and cation intercalation compounds and charge transfer processes are the driving forces for their formation. 

As can be appreciated in the examples illustrated in Table 4.14, a number of superconductors based on the inclusion of alkali metals and thalium have been prepared. Superconducting transition temperatures in these compounds are significantly higher than those observed for the correponding graphite intercalates. Apparently, in the case of the fullerenes there is a near linear relationship between the superconducting transition temperature, Tp, and the alkali metal size. Such a relationship, deduced from the correlation between Tp and the... 

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