Solid state continued formation

This is only the beginning of a process which ultimately results in the formation of solid state hydroxides or oxides. Actually, the solution species present in neutral or alkaline solutions of transition-metal ions are relatively poorly characterized. The formation of numerous hydroxy- and oxy-bridged polynuclear species makes their investigation very difficult. However, it is clear that there is a near-continuous transition from mononuclear solution species, through polynuclear solution species to colloidal and solid state materials. By the way, the first example of a purely inorganic compound to exhibit chirality was the olated species 9.11. 

When the complex formation by solid-solid reaction is combined with a photoreaction in the solid state, a stereoselective photoreaction can be carried out continu-... 

Using specific metal combinations, electrodeposited alloys can be made to exhibit hardening as a result of heat treatment subsequent to deposition. This, it should be noted, causes solid precipitation. When alloys such as Cu-Ag, Cu-Pb, and Cu-Ni are coelectrodeposited within the limits of diffusion currents, equilibrium solutions or supersaturated solid solutions are in evidence, as observed by x-rays. The actual type of deposit can, for instance, be determined by the work value of nucleus formation under the overpotential conditions of the more electronegative metal. When the metals are codeposited at low polarization values, formation of solid solutions or of supersaturated solid solutions results. This is so even when the metals are not mutually soluble in the solid state according to the phase diagram. Codeposition at high polarization values, on the other hand, results, as a rule, in two-phase alloys even with systems capable of forming a continuous series of solid solutions. 

Lacking a meta constituent, it is clear that 19 alone cannot satisfy an analogous ring of continuous intermolecular interactions aroimd anthracene. Hence, no cocrystalhsation occurred by sohd-state grinding, and the incorporation of a benzene solvent molecule upon solution evaporation was necessary to permit cocrystalhsation (Fig. 4c). The authors thus attributed the lack of cocrystal formation by solid-state grinding to an inabihty of reactants to satisfy the desired intermolecular interactions, rather than the relative stabihty of reactants. 

Transition from non-metallic clusters consisting of only a few atoms to nanosized metallic particles consisting of thousands of atoms and the concomitant conversion from covalent bond to continuous band structures have been the subject of intense scrutiny in both the gas phase and the solid state during the last decade [503-505]. It is only recently that modern-day colloid chemists have launched investigations into the kinetics and mechanisms of duster formation and cluster aggregation in aqueous solutions. Steady-state and pulse-radiolytic techniques have been used primarily to examine the evolution of nanosized metallic particles in metal-ion solutions [506-508]. 

With the recognition that many substances may cocrystallize in a single continuous lattice structure, scientists have more recently initiated intense studies of the mixed molecular crystal systems that have become known as cocrystals [10]. This particular area of solid-state research has led pharmaceutical scientists into the areas of crystal engineering and assembly of appropriate supramolecular synthons, with particular emphasis on understanding the origins of the molecular self-assembly that takes place in the formation of cocrystal systems. 

Liquid clathrates offer a great advantage over solid-state separations (e.g. by formation of Hoffman-type inclusion compounds, Section 9.4) because of the extremely fast mixing kinetics, the avoidance of the need to wait for crystallisation to occur and the easy separation of the two liquid phases. It should also prove possible to run liquid clathrate separations in a continuous extraction manner. The avalues of a number of liquid clathrate-based separations have been reported and are summarised in Table 13.1. 

Direct observation of complex in the a-deprotonation of N,N-dimethylbenzamide and kinetic studies are interpreted in terms of a tetrameric cube-like transition state structure typical of solid-state RLi structures in which ligands bound to the Li centers facilitate the release of the a-carbanion species. The continuing existence of the RLi tetramer on addition of TMEDA contrasts with the dogma that this additive breaks up aggregates and is rationalized by TMEDA advancing the formation of the a-carbanion in the transition state analogous to the effect of the R carbanion character in the tetramer. 

Unlike the still-unknown 277-pyran which exists exclusively in the ring-opened form, 277-thiopyran is a well-characterized molecule. Nevertheless, the S-C(2) bond can be cleaved and this is the basis of the photochromic properties observed with spirobenzothiopyrans. Irradiation at 365 nm of the spiro[2/7-l-benzothiopyran-2,2 -indoline] 273 in both the solid state and in solution results in opening of the thiopyran ring and the formation of a colored metastable zwitterionic merocyanine (Equation 21). The open form exhibits solvatochromism, with Amax 588 nm in methanol and 673 nm in acetone. In solution, the thiopyran unit reforms rapidly when irradiation ceases, but continuous irradiation leads to the growth of crystals of the open form <2002JOC533>. 

---