Crystal structure-solid state reactivity

Ariel, S., Evans, S. V, Garcia-Garibay, M., Harkness, B. R., Omkaram, N., Scheffer, J. R., and Trotter, J., The generation of 1,4-biradicals in rigid media crystal structure—solid state reactivity correlation, J. Am. Chem. Soc., 110,5591, 1988. 

Crystal Structure-Solid-State Reactivity Relationships... 

In many respects, the present results resemble the pioneering work of the late G. M. J. Schmidt and his co-workers at the Weizmann Institute of Science, who used crystal structure-solid-state reactivity correlations to elucidate the geometric requirements for intermolecular [2+2]-photocycloaddition. In both his case and ours, distance and angular requirements for reaction were established and the structure and stereochemistry of the products were shown to be simply and directly related to the molecular structure existing in the bulk crystal. 

Byrn, S. R., Sutton, R A., Tobias, B., Frye, J. and Main, P. (1988). The crystal structure solid state NMR spectra and oxygen reactivity of five crystal forms of prednisolone tert-butylacetate. J. Am. Chem. Soc., 110, 1609-14. [135]... 

SR Byrn, PA Sutton, B Tobias, J Frye, P Main. Crystal structure, solid-state NMR spectra, and oxygen reactivity of five crystal forms of prednisolone ierf-butylace-tate. J Am Chem Soc 110 1609-1614, 1988. 

S. R. Byrn, P. A. Sutton, B. Tobias, J. Frye, and P. Main,/. Am. Chem. Soc., 110,1609 (1988). The Crystal Structure, Solid-State NMR Spectra, and Oxygen Reactivity of Five Crystal Forms of Prednisolone tert-Butylacetate. 

Fig. 39 Template-controlled solid-state reactivity, X-ray crystal structures of (a) four-component assembly 2(4-bn-res) 2(l,4-bpeb) (b) targeted cyclophane (c) four-component assembly 2(5-OMe-res) 2(l,6-bpht) and (d) targeted [5]-ladderane.

Matsumoto, A., Furukawa, D., Mori, Y., Tanaka, T. and Oka, K. (2007) Change in crystal structure and polymerization reactivity for the solid-state polymerization of muconate esters. Cryst. Growth Des., 7, 1078-1085. 

The solid state reactivity of butadiene derivatives has first been investigated by G.N.J. Schmidt and coworkers (1-1). They observed for a number of 1,4-disubstituted compounds that exposure to UV light leads to the formation of dimers according to a (2 2]-cycloaddition reaction. The structure of the dimers was found to be strictly related to the monomer arrangement in the crystal lattice. Oligomers or polymers could only be obtained as side products. 

Many aspects of the preparation and properties of polydiacetylenes are the subject of lively debate. This review presents recent results that bear on some of these controversies. First the relationship of diacetylene monomer crystal structure and solid-state reactivity is discussed. Secondly the temporal evolution of solvato-chromio transitions of soluble polydiacetylenes is displayed. Optical and Raman spectra reveal the occurrence of an intermediate form of the polymer. A model compatible with these results is described. 

The crystal structure of 69 is 3D-interlocked leaving only rectangular channels that appear too narrow (Fig. 2.1.54) to enable molecular migrations and thus no solid-state reactivity is to be expected for this drug either. While these judgments... 

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