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: | 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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