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

Paul Raithby, Lauren Hatcher

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5 Citations (Scopus)


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.
Original languageEnglish
Pages (from-to)6297-6304
Number of pages9
Issue number42
Publication statusPublished - 11 Sep 2017



  • Photocrystallography
  • linkage isomers
  • palladium
  • hydrogen bnding

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