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Correlation studies in organic solids

As for solids. .. in order that among their molecules or particles be made such a tight binding as is cause of their compactness, it is necessary that they may be located in certain given ways, which are appropriate for cohesion to exert its energy. [Pg.196]

Translated from G.Brugnatelli, Trattato delle Cose Naturali e dei loro Ordini Conservatori, 1837 Pavia, Tipografia Tizzoni, Vol. I, p. 34. [Pg.196]

The attractive forces acting between the atoms will cause the portions of space which they respectively appropriate. .. to be in contact with one another, at the maximum number of points and as a result... the molecules themselves will also pack closely together... [Pg.196]


Olovsson, G., Scheffer, J. R., and Trotter, J. (1997) Determination of the Absolute Steric Course of an Enantioselective Single Crystal-to-Single Crystal Photorearrangement, J. Am. Chem. Soc., 119, 1462-1463,. (e) Leibovitch, M., Olovsson, G., Scheffer, J. R., and Trotter, J. (1997) Absolute configuration correlation studies in solid state organic photochemistry, PureAppl. Chem., 69, 815-823. [Pg.131]

At least two correlation studies on the aqueous solubilities of liquid organic compounds have been published [18, 19], and in each case an excellent correlation (r > 0.9) was obtained. For both liquid and solid compounds, log P or CLOGP accounts for a major portion of variance in water solubility [3, 4, 20]. However, the... [Pg.233]

For decades such adsorption had been assumed to involve dipole interactions and interacting sites were termed "polar." It is quite clear in the above studies that dipoles in the polymers and in the solid surfaces do not contribute measurably to adsorption. Even from carbon tetrachloride, the solvent most favorable to adsorption, the amount of basic polymer (PMMA) that adsorbed onto basic calcium carbonate was only 2.5% of the amount that adsorbed on the same area of silica surface. Similarly, the amount of acidic polymer (CPVC) that adsorbed onto the acidic silica from any of the six solvents was less than 0.2% of the amount that adsorbed from carbon tetrachloride or dichloromethane onto the same area of basic calcium carbonate. It is concluded that adsorption of organic acids or bases from neutral organic solvents onto inorganic solids is governed entirely by acid-base interactions and is quite independent of dipole phenomena. It is therefore proposed that heats of adsorption are actually enthalpies of acid-base interaction and should therefore be subject to the Drago correlation ... [Pg.82]

Based on some interesting reactions in certain inorganic crystalline compounds, Kohlschutter [9,10] proposed that the nature and properties of the products obtained take place on the surface or within the solid state. Indeed, he coined the term topochemistry for such reactions in the solid state. However, systematic investigations of photoinduced reactions in crystals began from 1964 onward by Schmidt and Cohen [11], Their studies on the 2tt + 2tt photoreaction of cinnamic acid derivatives in the crystalline state and correlation with the molecular organization in these crystals led to what are now known as Topochemical Principles. The most important conclusions reached by them are as follows (1) The necessary conditions for the reactions to take place are that the reactive double bonds are parallel to one another and the center-to-center distance be within 4.1 A (2) there is one-to-one correspondence between the stereochemistry of the photoproduct and the symmetry relationship between the reactants. The centrosymmet-ric relationship (called the a-form) leads to centrosymmetric cyclobutane (anti-HT), whereas the mirror symmetric arrangements (called the (5-form) produce mirror symmetric dimer (yy -HH). [Pg.428]

Among several indicators of motional state of organic solids H linewidths has been used from very beginning of solid-state NMR. However, inherently low resolution of H MAS NMR spectra caused by the very strong homonuclear interactions and relatively low MAS speed lead to a very limited application of H MAS NMR for studies of mobility.1 A 2D wideline separation (WISE) experiment correlates carbon chemical shifts recorded under MAS with broad H lines.1,24 As a result a broad ll lines are separated in the components corresponding to the 13C sites in their close proximity. For mobile domains in a sample, the H - ll coupling are relatively weak which leads to relatively narrow 11 static lines. The opposite is observed for the rigid domains. [Pg.269]

In multidimensional NMR studies of organic compounds, 2H, 13C and 31P are suitable probe nuclei.3,4,6 For these nuclei, the time evolution of the spin system is simple due to 7 1 and the strengths of the quadrupolar or chemical shift interactions exceed the dipole-dipole couplings so that single-particle correlation functions can be measured. On the other hand, the situation is less favorable for applications on solid-ion conductors. Here, the nuclei associated with the mobile ions often exhibit I> 1 and, hence, a complicated evolution of the spin system requires elaborate pulse sequences.197 199 Further, strong dipolar interactions often hamper straightforward analysis of the data. Nevertheless, it was shown that 6Li, 7Li and 9Be are useful to characterize ion dynamics in crystalline ion conductors by means of 2D NMR in frequency and time domain.200 204 For example, small translational diffusion coefficients D 1 O-20 m2/s became accessible in 7Li NMR stimulated-echo studies.201... [Pg.283]

For solid solutes a hypothetical value of 62 can be calculated from (U/V) where U is in this case the lattice energy of the crystal. In a study of the solubility of ion pairs in organic solvents it has been found that the logarithm of the solubility (log S) correlates well with 6,-62). ... [Pg.157]


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