Extended covalent arrays

Two later sections (1.6.5 and 1.6.6) look at the crystalline structures of covalently bonded species. First, extended covalent arrays are investigated, such as the structure of diamond—one of the forms of elemental carbon—where each atom forms strong covalent bonds to the surrounding atoms, forming an infinite three-dimensional network of localized bonds throughout the crystal. Second, we look at molecular crystals, which are formed from small, individual, covalently-bonded molecules. These molecules are held together in the crystal by weak forces known collectively as van der Waals forces. These forces arise due to interactions between dipole moments in the molecules. Molecules that possess a permanent dipole can interact with one another (dipole-dipole interaction) and with ions (charge-dipole interaction). Molecules that do not possess a dipole also interact with each other because transient dipoles arise due to the movement of electrons, and these in turn induce dipoles in adjacent molecules. The net result is a weak attractive force known as the London dispersion force, which falls off very quickly with distance. 

Extended covalent array Atoms Mainly covalent Strong hard crystals of high m.t. insulators Diamond, silica... 

Elements. Those elements that form extended covalent (as opposed to metallic) arrays are boron, all the Group IV elements except lead, also phosphorus, arsenic, selenium and tellurium. All other elements form either only metallic phases or only molecular ones. Some of the above elements, of course, have allotropes of metallic or molecular type in addition to the phase or phases that are extended covalent arrays. For example, tin has a metallic allotrope (white tin) in addition to that with the diamond structure (grey tin), and selenium forms two molecular allotropes containing Se8 rings, isostruc-... 

Oxygen and nitrogen, for example, form diatomic molecules which do not, in the solid state, participate in more extended covalent arrays like the continuous spirals of selenium. This is because, for specific reasons, the diatomic molecules are very stable. The double link of the oxygen molecule is in fact more than twice as strong as the single link. Thus a large number of separate O2 molecules are more stable than a long chain—0—0—O—0—0—O—. 

All substances, except helium, if cooled sufficiently form a solid phase the vast majority form one or more crystalline phases, where the atoms, molecules, or ions pack together to form a regular repeating array. This book is concerned mostly with the structures of metals, ionic solids, and extended covalent structures structures which do not contain discrete molecules as such, but which comprise extended arrays of atoms or ions. We look at the structure and bonding in these solids, how the properties of a solid depend on its structure, and how the properties can be modified by changes to the structure. 

The Fullerenes form particularly strong complexes with porphyrins as exemplified by the X-ray crystal structure of the covalent Fullerene-porphyrin conjugate 15.8 (Figure 15.29).48 This property allows fullerenes and porphyrins to form extended supramolecular arrays (even when not covalently linked) and has been used to engineer host-guest complexes in which a Fullerene is sandwiched in between a pair of porphyrins, and ordered arrays involving interleaved porphyrins and Fullerenes. Applications include the use of porphyrin solid phases in the chromatographic separation of Fullerenes and potential applications in porous frameworks and photovoltaic devices.49... 

In a different approach, fluorescence-based DNA microarrays are utilized (88). In a model study, chiral amino acids were used. Mixtures of a racemic amino acid are first subjected to acylation at the amino function with formation of A-Boc protected derivatives. The samples are then covalently attached to amine-functionalized glass slides in a spatially arrayed manner (Fig. 10). In a second step, the uncoupled surface amino functions are acylated exhaustively. The third step involves complete deprotection to afford the free amino function of the amino acid. Finally, in a fourth step, two pseudo-Qn nX. om.Qx c fluorescent probes are attached to the free amino groups on the surface of the array. An appreciable degree of kinetic resolution in the process of amide coupling is a requirement for the success of the ee assay (Horeau s principle). In the present case, the ee values are accessible by measuring the ratio of the relevant fluorescent intensities. About 8000 ee determinations are possible per day, precision amounting to +10% of the actual value ((S(S). Although it was not explicitly demonstrated that this ee assay can be used to evaluate enzymes (e.g., proteases), this should in fact be possible. So far this approach has not been extended to other types of substrates. 

Can the strategy of combining the sequence specificity of H bond arrays with reversible covalent interactions be extended into polar media To answer this question, strands 3 and 4 were modified with A-trityl end groups capable of reversibly forming disulfide bonds in the presence of iodine (Kamber et al. 1980), leading to complementary strands 19 and 20 (Fig. 9.14a Li et al. 2006). 

Finally, we consider crystal structures that do not contain any extended arrays of atoms. The example of graphite in the previous section in a way forms a bridge between these structures and the structures with infinite three-dimensional arrays. Many crystals contain small, discrete, covalently bonded molecules that are held together only by weak forces. 

By far the most important network covalent solids are the silicates. They utilize a variety of bonding patterns, but nearly all consist of extended arrays of covalently bonded silicon and oxygen atoms. Quartz (Si02) is a common example. We ll discuss silicates, which form the structure of clays, rocks, and many minerals, when we consider the chemistry of silicon in Chapter 14. 

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