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Coordinative alignment of molecules in chiral metal-organic frameworks

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Science  19 Aug 2016:
Vol. 353, Issue 6301, pp. 808-811
DOI: 10.1126/science.aaf9135

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Stop wiggling and hold that pose

X-ray crystallography can be the definitive method for determining the structure and chirality of small organic molecules, but orientational disorder in the crystal can limit its resolution. Lee et al. used a chiral metal-organic framework containing formate ligands that can bind and align molecules covalently to reduce this motion (see the Perspective by Öhrström). The structure and absolute configuration—i.e., which spatial arrangement of atoms is the R or S isomer—of several organic molecules can thus be measured. These range from small molecules, such as methanol, to complex plant hormones, such as gibberellins that have eight stereocenters or jasmonic acid, whose absolute configuration had not previously been directly established.

Science, this issue p. 808; see also p. 754

Abstract

A chiral metal-organic framework, MOF-520, was used to coordinatively bind and align molecules of varying size, complexity, and functionality. The reduced motional degrees of freedom obtained with this coordinative alignment method allowed the structures of molecules to be determined by single-crystal x-ray diffraction techniques. The chirality of the MOF backbone also served as a reference in the structure solution for an unambiguous assignment of the absolute configuration of bound molecules. Sixteen molecules representing four common functional groups (primary alcohol, phenol, vicinal diol, and carboxylic acid), ranging in complexity from methanol to plant hormones (gibberellins, containing eight stereocenters), were crystallized and had their precise structure determined. We distinguished single and double bonds in gibberellins, and we enantioselectively crystallized racemic jasmonic acid, whose absolute configuration had only been inferred from derivatives.

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