Defects topochemical

Oxidative catalysis over metal oxides yields mainly HC1 and C02. Catalysts such as V203 and Cr203 have been used with some success.49 50 In recent years, nanoscale MgO and CaO prepared by a modified aerogel/hypercritical drying procedure (abbreviated as AP-CaO) and AP-MgO, were found to be superior to conventionally prepared (henceforth denoted as CP) CP-CaO, CP-MgO, and commercial CaO/MgO catalysts for the dehydrochlorination of several toxic chlorinated substances.51 52 The interaction of 1-chlorobutane with nanocrystalline MgO at 200 to 350°C results in both stoichiometric and catalytic dehydrochlorination of 1-chlorobutane to isomers of butene and simultaneous topochemical conversion of MgO to MgCl2.53-55 The crystallite sizes in these nanoscale materials are of the order of nanometers ( 4 nm). These oxides are efficient due to the presence of high concentration of low coordinated sites, structural defects on their surface, and high-specific-surface area. 

Electronic excitation energy in a crystal is in many cases highly mobile It may diffuse very rapidly through many thousands of molecules and eventually be trapped at some appropriate defect site. If, then, photoreaction occurs at this site, the stereochemistry of the reaction pathway will be determined by the symmetry of this site, and not by the symmetry of the bulk crystal. Nevertheless, the bulk symmetry is found empirically to be the determining factor in most cases studied (topochemical control). 

There are a number of possible explanations for the formation of more than one photodimer. First, due care is not always taken to ensure that the solid sample that is irradiated is crystallographically pure. Indeed, it is not at all simple to establish that all the crystals of the sample that will be exposed to light are of the same structure as the single crystal that was used for analysis of structure. A further possible cause is that there are two or more symmetry-independent molecules in the asymmetric unit then each will have a different environment and can, in principle, have contacts with neighbors that are suited to formation of different, topochemical, photodimers. This is illustrated by 61, which contrasts with monomers 62 to 65, which pack with only one molecule per asymmetric unit. Similarly, in monomers containing more than one olefinic bond there may be two or more intermolecular contacts that can lead to different, topochemical, dimers. Finally, any disorder in the crystal, for example due to defective structure or molecular-orientational disorder, can lead to formation of nontopochemical products in addition to the topochemical ones formed in the ordered phase. This would be true, too, in those cases where there is reaction in the liquid phase formed, for example, by local melting. 

Eq. 2-248) [Braun and Wegner, 1983 Hasegawa et al., 1988, 1998]. This polymerization is a solid-state reaction involving irradiation of crystalline monomer with ultraviolet or ionizing radiation. The reaction is a topochemical or lattice-controlled polymerization in which reaction proceeds either inside the monomer crystal or at defect sites where the product structure and symmetry are controlled by the packing of monomer in the lattice or at defect sites, respectively. 

In the absence of defects, the reactivity of organic solids is mainly determined by molecular packing. Reactions in which the crystal structure holds sway over intrinsic molecular reactivity are said to be topochemically controlled (Thomas, 1974). A classic example of a topochemically controlled organic reaction in the solid state is the photodimerization of rrans-cinnamic acids studied by Schmidt et al. (see Ginsburg,... 

Figure 4 Duration of irradiation versus yield-irradiation time given in hours for 7-methoxycoumarin and 7-chlorocoumarin (topochemical reaction) irradiation in days for 4-methyl-6-chlorocoumarin (defect-initiated reaction)...

Most solid state work published in recent years has dealt primarily with a molecular analysis of product formation that seems to arise from the intuitive appeal of the topochemical postulate. Problems associated with phase changes can sometimes be neglected if reactions are carried out to sufficiently low conversion values. However, since preferential reactions at defect sites may be a problem, the involvement of nontopochemical reactions at defect sites should be experimentally documented and avoided. Changes in reaction rates and product selectivity have also been associated with internal stress [54], with sample melting, or with surface effects [62]. In contrast, the mechanisms and consequences of phase transformation have been studied much less. Phase changes depend on the properties of the ensemble and, as suggested in Scheme 5, they are affected by composition, temperature, pressure and whether or not equilibrium is achieved throughout the reaction. 

Some important aspects of topochemical polymerizations can be understood by inspection of Eq. (1), All reactivity comes about by very specific rotations of the monomers and by 1,4-addition of adjacent units and an extended, fully conjugated polymer chain is formed. The unique feature of the topochemical polymerization of diacetylenes is the fact that in many cases the reaction can be carried out as a single phase process. This leads to macroscopic, defect-free polymer single crystals which cannot be obtained, in principle, by crystallization of ready-made polymers by conventional methods. Thus, polydiacetylenes are ideal models for the investigation of the behaviour of macromolecules in their perfect three dimensional crystal lattice. 

Apart from the uniqueness of the reaction the morphology of the product depends substantially on the distribution of the reaction centers in the crystal. Two limiting cases can be considered. In the case of a heterogeneous topochemical process the reaction starts preferentially at specific defect sites and proceeds with nucleation of product phases. This mechanism eventually leads to the destruction of the mother crystal since the coherence between the various nuclei is lost under the influence of... 

In 1964, G.M.J. Schmidt and collaborators (7,8) enunciated the topochemical principle, a structural concept which notes that grouprs undergoing reaction in the solid state should be close ( 4.0 angstroms) and further emphasized reactivity in the ordered lattice rather than at defects. 

The essence of this phenomenon is that properties of defect clustered centers and kinetic features of the oxidation reactions depend upon stoichiometry of the surface layer. For oxides studied, surface reduction is a topochemical type process and proceeds via spreading of the reduced zone from the extended surface defects accompanied by a cations redistribution between the regular and the interstitial positions. Reoxidation as well as hydroxylation/carbonization causes shrinkage of this zone. 

General Considerations. In the well-known photodimerization of anthracenes in liquid solution 9, lO /lO, 9 -dimers (head-to-tail [4 + 4]) are formed in most cases. However, there have also been instances where head-to-head-photodimers (9,9 /10,10 ) are produced [19], and these were overseen previously. The solid phase photoreactions of anthracenes charged the topochemical postulate [7] for decades with hitherto unsolvable difficulties. All examples that contradict this assumption were eliminated without hesitation from the scope of topochemistry and termed to be crystal defect reactions, because the topochemically allowed processes were taken as support for topochemistry without further proof. The later provision, that the dimerizations occur within reaction cavities in the bulk of the crystal [20], did not help in this respect. A summary of the various arguments is given in Ref. 8. From examples 7 to 8 only b and perhaps c formally meet... 

When I was young, solid-state phase changes and chemical reactions were regarded more as a nuisance than as an area worthy of serious study and attention. It was the topochemical approach to solid-state chemical reactions, pioneered by Gerhard Schmidt, that transformed the subject for me and for many others. The textbook example is the photochemical dimerization of (fj-cinnamic acids in solution such compounds yield mixtures of the various possible stereoisomeric products, but irradiation of a particular crystal leads to a single product, or to no reaction, depending on the crystal structure [40]. Thus, one can determine the relative positions of the atoms before the reaction and after it, and haice deduce the metrical relationships that needed to be satisfied for reaction to proceed. In the meantime we have learned that not all chemical reactions in solids are topochemical. Some proceed not in the ordered bulk of the crystal but at defects, on the surface, or at other irregularities. 

However, Fierens [9] has shown, that the hydroxylation of the slag glass surface layer, as a result of water molecules chemisorption, which is enhanced by the surface electron defects (trapped electrons), can be considered as a topochemical process. The topochemical processes became important also at later hydration stage, when the pozzolanic reaction of slag glass network, impoverishes of the majority of alkaline elements, with calcium ions is occtrrring, and calcium ions are chemisorbed on the active sites of solid phase. 

---