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Issue 30, 2020
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The crystal engineering of radiation-sensitive diacetylene cocrystals and salts

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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 4,4′-azopyridine (2), 4,4′-bipyridyl (3), and trans-1,2-bis(4-pyridyl)ethylene (4) results in unreactive 2 : 1 cocrystals or a salt in the case of 4,4′-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 γ-ray dosimetry applications.

Graphical abstract: The crystal engineering of radiation-sensitive diacetylene cocrystals and salts

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Article information


Submitted
05 May 2020
Accepted
18 Jul 2020
First published
20 Jul 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 8025-8035
Article type
Edge Article

The crystal engineering of radiation-sensitive diacetylene cocrystals and salts

A. V. Hall, D. S. Yufit, D. C. Apperley, L. Senak, O. M. Musa, D. K. Hood and J. W. Steed, Chem. Sci., 2020, 11, 8025 DOI: 10.1039/D0SC02540B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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