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Issue 42, 2017
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The impact of hydrogen bonding on 100% photo-switching in solid-state nitro–nitrito linkage isomers

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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.

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

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Publication details

The article was received on 25 Jul 2017, accepted on 06 Sep 2017 and first published on 11 Sep 2017


Article type: Paper
DOI: 10.1039/C7CE01366C
Citation: CrystEngComm, 2017,19, 6297-6304
  • Open access: Creative Commons BY-NC license
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    The impact of hydrogen bonding on 100% photo-switching in solid-state nitro–nitrito linkage isomers

    L. E. Hatcher and P. R. Raithby, CrystEngComm, 2017, 19, 6297
    DOI: 10.1039/C7CE01366C

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