A mechanophysical phase transition provides a dramatic example of colour polymorphism: the tribochromism of a substituted tri(methylene)tetrahydrofuran-2-one

BACKGROUND: Derivatives of fulgides have been shown to have interesting photochromic properties. We have synthesised a number of such derivatives and have found, in some cases, that crystals can be made to change colour on crushing, a phenomenon we have termed "tribochromism". We have studied a number of derivatives by X-ray crystallography, to see if the colour is linked to molecular structure or crystal packing, or both, and our structural results have been supported by calculation of molecular and lattice energies. RESULTS: A number of 5-dicyanomethylene-4-diphenylmethylene-3-disubstitutedmethylene-tetrahydrofuran-2-one compounds have been prepared and structurally characterised. The compounds are obtained as yellow or dark red crystals, or, in one case, both. In two cases where yellow crystals were obtained, we found that crushing the crystals gave a deep red powder. Structure determinations, including those of the one compound which gave both coloured forms, depending on crystallisation conditions, showed that the yellow crystals contained molecules in which the structure comprised a folded conformation at the diphenylmethylene site, whilst the red crystals contained molecules in a twisted conformation at this site. Lattice energy and molecular conformation energies were calculated for all molecules, and showed that the conformational energy of the molecule in structure IIIa (yellow) is marginally higher, and the conformation thus less stable, than that of the molecule in structure IIIb (red). However, the van der Waals energy for crystal structure IIIa, is slightly stronger than that of structure IIIb - which may be viewed as a hint of a metastable packing preference for IIIa, overcome by the contribution of a more stabilising Coulomb energy to the overall more favourable lattice energy of structure IIIb. CONCLUSIONS: Our studies have shown that the crystal colour is correlated with one of two molecular conformations which are different in energy, but that the less stable conformation can be stabilised by its host crystal lattice. Graphical abstractGraphical representation of the structural and colour change in the tribochromic compound (III)

Radical-cation salts of BEDT-TTF with lithium tris(oxalato)metallate(III)

The first radical-cation salts in the extensive family (BEDT-TTF)x[(A)M(C2O4)3]·Guest containing lithium as the counter cation have been synthesized and characterised

α-Allylation of α-amino acids via 1,5-hydrogen atom transfer

Copyright © 2009 Elsevier. NOTICE: this is the author’s version of a work that was accepted for publication in Tetrahedron Letters. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Tetrahedron Letters, 2009, Vol. 50, Issue 26, pp. 3400 – 3403 DOI: http://dx.doi.org/10.1016/j.tetlet.2009.02.110A straightforward method for the radical-based α-allylation of proteinogenic α-amino acids is described in which the key step involves 1,5-hydrogen atom transfer from the C-4 position of an oxazolidin-5-one

Synthetic use of the primary kinetic isotope effect in hydrogen atom transfer: generation of α-aminoalkyl radicals.

addresses: School of Biosciences, University of Exeter, Geoffrey Pope Building, Stocker Road, Exeter, UKEX4 4QD. [email protected]: Journal Article; Research Support, Non-U.S. Gov'tCopyright © 2010 Royal Society of ChemistryThe extent to which deuterium can act as a protecting group to prevent unwanted 1,5-hydrogen atom transfer to aryl and vinyl radical intermediates was examined in the context of the generation of α-aminoalkyl radicals in a pyrrolidine ring. Intra- and intermolecular radical trapping following hydrogen atom transfer provides an illustration of the use of the primary kinetic isotope effect in directing the outcome of synthetic C-C bond-forming processes