Autor: |
Bertran A; Centre for Advanced Electron Spin Resonance and Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, UK., Ciuti S; Department of Chemical Sciences, University of Padova, Via Marzolo 1, Padova 35131, Italy. antonio.barbon@unipd.it.; Department of Chemistry, Photon Science Institute and The National Research Facility for Electron Paramagnetic Resonance, University of Manchester, Oxford Road, Manchester M13 9PL, UK. alice.bowen@manchester.ac.uk., Panariti D; Department of Chemical Sciences, University of Padova, Via Marzolo 1, Padova 35131, Italy. antonio.barbon@unipd.it., Rogers CJ; Department of Chemistry, Photon Science Institute and The National Research Facility for Electron Paramagnetic Resonance, University of Manchester, Oxford Road, Manchester M13 9PL, UK. alice.bowen@manchester.ac.uk., Wang H; State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, P. R. China., Zhao J; State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, P. R. China., Timmel CR; Centre for Advanced Electron Spin Resonance and Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, UK., Gobbo M; Department of Chemical Sciences, University of Padova, Via Marzolo 1, Padova 35131, Italy. antonio.barbon@unipd.it., Barbon A; Department of Chemical Sciences, University of Padova, Via Marzolo 1, Padova 35131, Italy. antonio.barbon@unipd.it., Di Valentin M; Department of Chemical Sciences, University of Padova, Via Marzolo 1, Padova 35131, Italy. antonio.barbon@unipd.it., Bowen AM; Department of Chemistry, Photon Science Institute and The National Research Facility for Electron Paramagnetic Resonance, University of Manchester, Oxford Road, Manchester M13 9PL, UK. alice.bowen@manchester.ac.uk. |
Abstrakt: |
Electron paramagnetic resonance (EPR) pulsed dipolar spectroscopy (PDS) using triplet states of organic molecules is a growing area of research due to the favourable properties that these transient states may afford over stable spin centers, such as switchability, increased signal intensity when the triplet is formed in a non-Boltzmann distribution and the triplet signal is used for detection, and high orientation selection, when the triplet signal is probed by microwave pulses. This arises due to the large spectral width at low fields, a result of the large zero field splitting, and limited bandwidth of microwave pulses used. Here we propose the triplet state of a substituted BODIPY moiety as a spin label in light induced PDS, coupled to a nitroxide, in a model peptide with a rigid structure. Orientation selection allows information on the relative position of the centres of the two labels to be obtained with respect to the nitroxide reference frame. Additionally, magnetophotoselection effects are employed to introduce optical selection and additional constraints for the determination of the relative orientation of the spin labels considering the reference frame of the triplet state. |