Metastable-State Photoacids with Fast Reverse Reactions

Rana Abbood; Shahriar N. Khan; Pavithra Liyanage; Zhuozhi Wang; Dmytro Bykov; Vyacheslav S. Bryantsev; Yi Liao

doi:10.1002/cptc.202500223

Metastable-State Photoacids with Fast Reverse Reactions

Rana Abbood
, Shahriar N. Khan
, Pavithra Liyanage
, Zhuozhi Wang
, Dmytro Bykov
, Vyacheslav S. Bryantsev
, Yi Liao

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Metastable-state photoacid (mPAH) has become a common tool for controlling and driving chemical processes with light. mPAHs with fast reverse reactions are desirable for precise temporal control or generating quick pulses of proton concentration. In this work, different approaches towards fast reversing mPAHs are studied. Experimental and computational results showed that stabilizing the charge–transfer intermediate is an effective way to increase the rate. A novel mPAH with a reverse reaction ≈500 times faster than the most used mPAH in methanol is developed. Another water-soluble mPAH showed a reverse reaction with a rate constant of 7.8 s⁻¹, which is the fastest ever reported. The half-life of the acidic state is calculated to be 89 ms, which allowed to demonstrate sub-second switching using this mPAH.

Original language	English
Article number	e202500223
Journal	ChemPhotoChem
Volume	10
Issue number	1
DOIs	https://doi.org/10.1002/cptc.202500223
State	Published - Jan 2026

Funding

This research was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Separation Sciences. under contract no. AC05-00OR22725. This research used resources of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under contract no. DE-AC05-00OR22725. This research was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Separation Sciences. under contract no. AC05‐00OR22725. This research used resources of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under contract no. DE‐AC05‐00OR22725.

Keywords

pH control
photoacid
photoswitch

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10.1002/cptc.202500223

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title = "Metastable-State Photoacids with Fast Reverse Reactions",

abstract = "Metastable-state photoacid (mPAH) has become a common tool for controlling and driving chemical processes with light. mPAHs with fast reverse reactions are desirable for precise temporal control or generating quick pulses of proton concentration. In this work, different approaches towards fast reversing mPAHs are studied. Experimental and computational results showed that stabilizing the charge–transfer intermediate is an effective way to increase the rate. A novel mPAH with a reverse reaction ≈500 times faster than the most used mPAH in methanol is developed. Another water-soluble mPAH showed a reverse reaction with a rate constant of 7.8 s−1, which is the fastest ever reported. The half-life of the acidic state is calculated to be 89 ms, which allowed to demonstrate sub-second switching using this mPAH.",

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AU - Abbood, Rana

AU - Khan, Shahriar N.

AU - Liyanage, Pavithra

AU - Wang, Zhuozhi

AU - Bykov, Dmytro

AU - Bryantsev, Vyacheslav S.

AU - Liao, Yi

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AB - Metastable-state photoacid (mPAH) has become a common tool for controlling and driving chemical processes with light. mPAHs with fast reverse reactions are desirable for precise temporal control or generating quick pulses of proton concentration. In this work, different approaches towards fast reversing mPAHs are studied. Experimental and computational results showed that stabilizing the charge–transfer intermediate is an effective way to increase the rate. A novel mPAH with a reverse reaction ≈500 times faster than the most used mPAH in methanol is developed. Another water-soluble mPAH showed a reverse reaction with a rate constant of 7.8 s−1, which is the fastest ever reported. The half-life of the acidic state is calculated to be 89 ms, which allowed to demonstrate sub-second switching using this mPAH.

KW - pH control

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KW - photoswitch

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ER -

Metastable-State Photoacids with Fast Reverse Reactions

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