Abstract
The structures of several unstable or metastable reaction intermediates photoproduced in crystals were analyzed by using X-ray techniques. The presence of enough void space around the reactive group(s) is an essential factor for the reaction to occur with retention of the single-crystal form. To expand the void space, an acid carboxyl group (COOH) was substituted onto the reactant molecule and acid–base complex crystals were prepared with several amines, such as dibenzylamine and dicyclohexylamine. Following the formation of such acid–base complexes in crystals, the metastable structures of nitrenes and red species of photochromic salicylideneanilines have been successfully analyzed by using X-ray techniques. For a salicylideneaniline molecule, three polymorphic crystals were obtained, which showed different color changes. Moreover, the structure of a Pt complex anion in the excited state has been analyzed, which formed acid–base complex crystals with various alkylammonium cations. The formation of acid–base complexes will be a powerful tool for directly observing the structure of unstable or metastable reaction intermediates by using X-ray techniques.
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Ohashi, Y. (2014). Structure Analyses of Unstable Reaction Intermediates Using the Technique of Acid-Base Complex or Polymorphic Crystal Formation. In: Howard, J., Sparkes, H., Raithby, P., Churakov, A. (eds) The Future of Dynamic Structural Science. NATO Science for Peace and Security Series A: Chemistry and Biology. Springer, Dordrecht. https://doi.org/10.1007/978-94-017-8550-1_15
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DOI: https://doi.org/10.1007/978-94-017-8550-1_15
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