Coherent Polarization Transfer Effects Are Crucial for Interpreting Low-Field CIDNP Data
In this work we demonstrate that low-field chemically induced dynamic nuclear polarization (CIDNP) is strongly affected by re-distribution of polarization, which is formed in the course of spin evolution in transient radical pairs, in diamagnetic reaction products. This phenomenon is of importance when the spins of the reaction product are coupled strongly meaning that spin–spin interactions between them are comparable to the differences in their Zeeman interactions with the external magnetic field. In this case, polarization transfer relies on a coherent mechanism; as a consequence, spins can acquire significant polarization even when they have no hyperfine coupling to the electron spins in the radical pairs, i.e., cannot be polarized directly by CIDNP. This is demonstrated by taking CIDNP of n-butylamine as an example: in this case only the α-CH2 protons are polarized directly, which is confirmed by high-field CIDNP, whereas the β-CH2, γ-CH2 and δ-CH3 protons get polarized only indirectly due to the transfer of polarization from the α-CH2 protons. These results show that low-field CIDNP data should be interpreted with care to discriminate between the effects of spin evolution in transient radical pairs and in diamagnetic reaction products.
KeywordsPolarization Transfer Spin Dynamic Chemically Induce Dynamic Nuclear Polarization Spin Evolution Zeeman Interaction
We acknowledge financial support by the Russian Foundation for Basic Research (Grants No. 13-03-00437 and 14-03-00397), the CPRF Grant MD-3279.2014.2, the Research Group Linkage Program of the Alexander von Humboldt Foundation and the EU-COST Action TD1103.
- 1.K.M. Salikhov, Y.N. Molin, R.Z. Sagdeev, A.L. Buchachenko, Spin Polarization and Magnetic Effects in Chemical Reactions (Elsevier, Amsterdam, 1984)Google Scholar
- 3.A. Yurkovskaya, O. Morozova, G. Gescheidt, Encyclopedia of Radicals in Chemistry, Biology and Materials, vol. 1 (Wiley, New York, 2012), pp 175–206Google Scholar
- 9.A. G. Palmer III, W. J. Fairbrother, J. Cavanagh, N. J. Skelton, M. Rance, Protein NMR Spectroscopy: Principles and Practice, 2nd edn. (Academic Press, 2005)Google Scholar