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

Hall, Amy V. and Yufit, Dmitry S. and Apperley, David C. and Senak, Larry and Musa, Osama M. and Hood, David K. and Steed, Jonathan W. (2020) 'The crystal engineering of radiation-sensitive diacetylene cocrystals and salts.', Chemical science., 11 (30). pp. 8025-8035.

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.

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Status:Peer-reviewed
Publisher Web site:https://doi.org/10.1039/D0SC02540B
Publisher statement:This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Date accepted:18 July 2020
Date deposited:25 August 2020
Date of first online publication:20 July 2020
Date first made open access:25 August 2020

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