Abstract
Solid-state reactions are influenced by the spatial arrangement of the reactants and the electrostatic environment of the lattice, which may enable lattice-directed chemical dynamics. Unlike the caging imposed by an inert matrix, an active lattice participates in the reaction, however, little evidence of such lattice participation has been gathered on ultrafast timescales due to the irreversibility of solid-state chemical systems. Here, by lowering the temperature to 80 K, we have been able to study the dissociative photochemistry of the triiodide anion (I3−) in single-crystal tetra-n-butylammonium triiodide using broadband transient absorption spectroscopy. We identified the coherently formed tetraiodide radical anion (I4•−) as a reaction intermediate. Its delayed appearance after that of the primary photoproduct, diiodide radical I2•−, indicates that I4•− was formed via a secondary reaction between a dissociated iodine radical (I•) and an adjacent I3−. This chemistry occurs as a result of the intermolecular interaction determined by the crystalline arrangement and is in stark contrast with previous solution studies.
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Acknowledgements
We thank A. G. Dijkstra and M. A. Kochman for helpful discussions, and D. S. Badali for contributions to the initial development of the transient absorption setup. This work was funded by the Max Planck Society with additional support from the Hamburg Centre for Ultrafast Imaging. G.C. acknowledges the support from the Alexander von Humboldt Foundation. D.M.R. and C.A.M. acknowledge the UK Car-Parrinello Consortium for allocation of computing time on the EPSRC high performance computing resource ARCHER (managed by the Edinburgh Parallel Computing Centre), the EaStCHEM Research Computing Facility and the University of Edinburgh ECDF facility.
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R.J.D.M. conceived the experiment. R.X. grew TBAT crystals and prepared samples for optical measurements; G.C. constructed and programmed the experimental setups and R.X. modified the setups for the current experiment; R.X. performed the measurements with contributions from G.C.; R.X. analysed and interpreted the data under the supervision of V.I.P and S.A.H.; D.M.R. and C.A.M. carried out the quantum chemical calculations and wrote the theory sections of the manuscript; R.X. wrote the manuscript with contributions from G.C. and V.I.P.; all authors contributed to editing the manuscript to its final form.
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Xian, R., Corthey, G., Rogers, D. et al. Coherent ultrafast lattice-directed reaction dynamics of triiodide anion photodissociation. Nature Chem 9, 516–522 (2017). https://doi.org/10.1038/nchem.2751
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DOI: https://doi.org/10.1038/nchem.2751
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