Solid-state reactivity, template-controlled

MacGillivray LR, Papaefstathiou GS, Friscic T, Hamilton TD, Bucar D-K, Chu Q, Varshney DB, Georgiev IG (2008) Supramolecular control of reactivity in the solid state from templates to ladderanes to metal-organic frameworks. Acc Chem Res 41 280-291... 

Our approach template-controlled solid-state reactivity 143... 

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.

The first small-molecule templates to control the [2+2] photodimerization in the solid state involved ditopic hydrogen-bond donors. The templates assembled olefins lined with pyridyl groups. The solid-state reactivity was, consequently, achieved within a cocrystal or a structurally homogeneous crystalline material that contains two or more neutral building blocks present in definite stoichiometric amounts. ... 

Supramolecular Control of Reactivity in the Solid State Using Linear Templates... 

MacGillivray, L. R. From Engineering Crystals to Engineering Molecules Emergent Consequences of Controlling Reactivity in the Solid State Using Linear Templates. Cryst. Eng. Commun. 2002, 4, 37-42. 

MacGillivray, L. R. Reid, J. L. Ripmeester, J. A. Supramolecular Control of Reactivity in the Solid State Using Linear Molecular Templates. J. Am. Chem. Soc. 2000, 122, 7817-7818. 

Papaefstathiou, G. S. Kipp, A. J. MacGillivray, L. R. Exploiting Modularity in Template-Controlled Synthesis a New Linear Template to Direct Reactivity Within Discrete Hydrogen-Bonded Molecular Assemblies in the Solid State. Chem. Commun. 2001, 2432-2433. 

Papaefstathiou. G.S. Kipp, A.J. MacGilliviay, L.R. Exploiting modularity in template-directed synthesis A new linear template to control reactivity within discrete hydrogen-bonded molecular assemblies in the solid state. Chern. Commun. 2001, 2462-2463. 

MacGillivray, L.R. From engineering crystals to engineering molecules Emergent consequences of controlling reactivity in the solid state using linear templates. Cryst. 27. Eng. Commun. 2002. 37-41. 

In general, photoinert auxiliary molecules have been used as templating agents to direct double bonds in parallel orientations of single olefins and with distances smaller than 4.2 A. These geometrical parameters are strictly required as previous steps in order to achieve the photoreaction via topochemical control and then the template must be liberated from the expected product. We envisage that an alternative way to increase the level of sophistication in the design of solid state reactions is the possibility to extend the self-assembly of two or more potentially reactive unsaturated molecules controlled by directional supramolecular synthons. 

Scheme 1 Schematic of strategy to control reactivity in the solid state using a template.

MacGillivray LR, Reid JL, Ripmeester JA (2000) Supramolecular control of reactivity in the solid state using linear molecular templates. J Am Chem Soc 122 7817... 

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