Crystal engineering Solids

Keywords Crystal engineering Solid-state photoreaction Topochemical polymerization Controlled radical polymerization Dimerization Isomerization Topotactic reaction... 

Desiraju, G.R. Crystal engineering solid state supramolecular synthesis. Curr. Opin. Solid State Mater. Sci. 1997, 2 (4), 451 54. 

Coppens, P., Ma, B., Gerlits, O., Zhang, Y. and Kulshrestha, P., Crystal engineering, solid-state spectroscopy and time-resolved diffraction, Cryst Eng Comm, 2002, 4, 302-309. 

Jones, A.G., Budz, I. and Mullin, I.W., 1987. Batch crystallization and solid-liquid separation of potassium sulphate. Chemical Engineering Science, 42, 619-629. 

Crystal engineering. Utilization of noncovalent intermolecular forces in the solid state to design new nanomaterials with desired functions. 

Both theoretical and experimental data (in the solid, liquid, and gas phases) prove that the tendency of halocarbons to work as XB donors decreases in the order I > Br > Cl [66-68]. Clearly, polarizability and not electronegativity plays a key role. 3-Halo-cyanoacetylene works as self-complementary module and the N X distance is beautifully consistent with the scale reported above, being 2.932, 2.978 and 2.984 A in the iodo, bromo and chloro derivatives, respectively [69,70]. The same trend is observed when a phenyl, rather than a triple bond, spaces the donor and acceptor sites. The N Br distance in 4-bromobenzonitrile is longer than in the 4-iodo derivative [71,72] and no XB is present in the chloro and fluoro analogues, wherein molecules are pinned by N H and X- H short contacts [73]. PFCs have a very poor tendency, if any, to work as XB donors [74-77] and no crystal engineering can be based on such tectons. However, F2 is a quite strong XB donor and several adducts have been described in the gas phase [11,18] (see also the chapter by Legon in this volume). 

Desiraju GR (1989) In Crystal engineering the design of organic solids. Elsevier, Amsterdam... 

Braga D, D Addario D, Giaffreda SL, Maini L, Polito M, Grepioni F (2005) Intra-Solid and Inter-Solid Reactions of Molecular Crystals a Green Route to Crystal Engineering. 254 71-94... 

Trask AV, Jones W (2005) Crystal Engineering of Organic Cocrystals by the Solid-State Grinding Approach. 254 41-70 Tuntulani T, see Suksai C (2005) 255 163-198... 

Cf. e.g. the reviews on Conformational Polymorphism by J. Berstein in Organic Solid State Chemistry (Ed. G. R. Desiraju), Elsevier Amsterdam 1987, p. 471 or by G. R. Desiraju, Crystal Engineering, Material Science Monographs 54, Elsevier, Amsterdam 1989, p. 285. 

Solid-State Supramolecular Chemistry Crystal Engineering , Comprehensive Supramolecular Chemistry, Vol. 6 (Eds. J. L. Atwood, J. E. D. Davies, D. D. MacNicol, F. Vogtle, K. S. Suslick), Pergamon, Oxford, 1996. 

G. R. Desiraju, Crystal Engineering. The Design of Organic Solids, Elsevier, Amsterdam, 1989. 

The exploitation of the reactivity of molecular crystals lies close to the origins of crystal engineering and is at the heart of the pioneering work of Schmidt [47a]. The idea is that of organizing molecules in the solid state using the principles of molecular recognition and self-assembly. Successful results have been obtained with bimolecular reactions, particularly [2+2] photoreactivity and cyclisation [47b,c]. Another important area is that of host-guest chemistry. 

B. Crystal Engineering Toward a Systematic Solid-State Chemistry.170... 

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