Skip to main content

Research Repository

Advanced Search

The crystal engineering of radiation-sensitive diacetylene cocrystals and salts

Hall, Amy V.; Yufit, Dmitry S.; Apperley, David C.; Senak, Larry; Musa, Osama M.; Hood, David K.; Steed, Jonathan W.

The crystal engineering of radiation-sensitive diacetylene cocrystals and salts Thumbnail


Authors

Amy V. Hall

Dmitry S. Yufit

David C. Apperley

Larry Senak

Osama M. Musa

David K. Hood



Abstract

In this work we develop photoreactive cocrystals/salts of a commercially-important diacetylene, 10,12- pentacosadiynoic acid (PCDA, 1) and report the first X-ray crystal structures of PCDA based systems. The topochemical reactivity of the system is modified depending on the coformer used and correlates with the structural parameters. Crystallisation of 1 with 4,40 -azopyridine (2), 4,40 -bipyridyl (3), and trans-1,2- bis(4-pyridyl)ethylene (4) results in unreactive 2 : 1 cocrystals or a salt in the case of 4,40 -bipiperidine (5). However, salt formation with morpholine (6), diethylamine (7), and n-butylamine (8), results in highly photoreactive salts 12$7 and 1$8 whose reactivity can be explained using topochemical criteria. The salt 1$6 is also highly photoreactive and is compared to a model morpholinium butanoate salt. Resonance Raman spectroscopy reveals structural details of the photopolymer including its conformational disorder in comparison to less photoactive alkali metal salts and the extent of solid state conversion can be monitored by CP-MAS NMR spectroscopy. We also report an unusual catalysis in which amine evaporation from photopolymerised PCDA ammonium salts effectively acts as a catalyst for polymerisation of PCDA itself. The new photoreactive salts exhibit more reactivity but decreased conjugation compared to the commercial lithium salt and are of considerable practical potential in terms of tunable colours and greater range in UV, X-ray, and g-ray dosimetry applications.

Citation

Hall, A. V., Yufit, D. S., Apperley, D. C., Senak, L., Musa, O. M., Hood, D. K., & Steed, J. W. (2020). The crystal engineering of radiation-sensitive diacetylene cocrystals and salts. Chemical Science, 11(30), 8025-8035. https://doi.org/10.1039/d0sc02540b

Journal Article Type Article
Acceptance Date Jul 18, 2020
Online Publication Date Jul 20, 2020
Publication Date 2020-08
Deposit Date Aug 5, 2020
Publicly Available Date Mar 28, 2024
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 11
Issue 30
Pages 8025-8035
DOI https://doi.org/10.1039/d0sc02540b

Files







You might also like



Downloadable Citations