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Amino proton donors in excited-state intramolecular proton-transfer reactions

Nature Reviews Chemistry volume 2, pages 131–143 (2018)Cite this article

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Abstract

Proton transfer involving site-specific hydrogen-bonding interactions is one of the most fundamental and important reactions in chemistry and biology. Deliberately triggering this reaction by photoexcitation enables unique and insightful mechanistic analyses. This Review describes a particularly effective method that involves exciting a photoacid containing both an amine and a basic residue and monitoring the ensuing excited-state intramolecular proton-transfer (ESIPT) reactions. Replacing a H atom on the amine with another substituent R modulates the acidity of the amine and allows for the excited-state hydrogen-bond strength to be tuned over a very broad range. In this way, one can draw empirical correlations between N−H bond distances, acidity, hydrogen-bond strength and the ESIPT kinetics and thermodynamics. For example, stronger intramolecular N−H···N hydrogen bonding leads to faster and more exergonic ESIPT. Tuning the amine and basic residues allows one to switch the ESIPT mechanism between the kinetic and thermodynamic regimes, such that molecules can generate ratiometric emission, which is suitable for white-light generation and two-colour imaging. The identity of the amine substituent R not only affects the acidity but can be differentially sensitive towards the local chemical environment. Thus, the R group transduces environmental changes into modified ESIPT rates and/or mechanisms. Such studies open new frontiers in the fundamental aspects of proton transfer in amines, as well as their largely unexplored potential applications.

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Fig. 1: An energy scheme for ESIPT and some prominent O–H-type and N–H-type emitters.
Fig. 2: Tuning ESIPT in 2-(2′-aminophenyl)benzothiazole (ABT) derivatives using substituent effects.
Fig. 3: Green fluorescent proteins have inspired the design of O–H-type and N–H-type emitters.
Fig. 4: Structures and photophysics of 10-aminobenzo[h]quinoline (ABQ) derivatives68.
Fig. 5: New N–H-type ESIPT molecules for unique applications.

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Acknowledgements

P.-T.C. and A.P.D. thank the Ministry of Science and Technology, Taiwan, for the financial support. A. Burger, V. Pivovarenko and M. Tukalo are acknowledged for reading the manuscript and making important comments.

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  1. Department of Chemistry, National Taiwan University, Taipei, Taiwan

    Chi-Lin Chen, Yi-Ting Chen & Pi-Tai Chou

  2. Palladin Institute of Biochemistry, National Academy of Sciences of Ukraine, Kyiv, Ukraine

    Alexander P. Demchenko

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Chen, CL., Chen, YT., Demchenko, A.P. et al. Amino proton donors in excited-state intramolecular proton-transfer reactions. Nat Rev Chem 2, 131–143 (2018). https://doi.org/10.1038/s41570-018-0020-z

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