The impact of hydrogen bonding on 100% photo-switching in solid-state nitro-nitrito linkage isomers

Hatcher, Lauren E. ORCID: https://orcid.org/0000-0002-1549-9727 and Raithby, Paul R. 2017. The impact of hydrogen bonding on 100% photo-switching in solid-state nitro-nitrito linkage isomers. CrystEngComm 19 (42) 10.1039/C7CE01366C

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Abstract

Two crystal systems: [Pd(Et4dien)(NO2)]OTf [1] and [Pt(Et4dien)(NO2)]OTf [2] (Et4dien = N,N,N′,N′-tetraethyldiethylene-triamine, OTf = trifluoromethanesulfonate) are investigated by steady-state photocrystallographic methods. Both structures contain intermolecular hydrogen bonds to the ground state nitro-(η1-NO2) isomer, which are previously shown to limit the achievable level of nitro → nitrito photo-conversion. Irradiation at 100 K induces a mixture of endo-ONO and exo-ONO isomers in 1 and 2, with overall incomplete photo-activation. In contrast, irradiation at higher temperatures leads to much higher conversion, with 100% excitation in 1 at 150 K. The results show that the detrimental effects of hydrogen bonding on the photo-reaction are overcome at higher temperature, adding a new dimension of control to the isomerisation process.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1466-8033
Date of First Compliant Deposit:	19 March 2020
Date of Acceptance:	6 September 2017
Last Modified:	06 May 2023 04:30
URI:	https://orca.cardiff.ac.uk/id/eprint/130503

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