期刊
CHEMICAL SCIENCE
卷 12, 期 12, 页码 4588-4598出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0sc07000a
关键词
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资金
- Netherlands Organization for Scientific Research (NWO-CW VIDI) [723.014.001]
- Slovak Research and Development Agency [SK-FR-19-0002]
- Campus France
- French Embassy in Slovakia [45091SF]
- Scientific Grant Agency of the Slovak Republic [VEGA 1/0562/20]
- Ministry of Education, Youth and Sports of the Czech Republic, Operational Programme for Research, Development and Education of the European Regional Development Fund [CZ.02.1.01/0.0/0.0/16_019/0000754]
- ERC (European Union) [683024]
- Agence National de la Recherche [ANR-19-CE29-0008]
- Research and Development Operational Programme - ERDF [ITMS 26230120002, 26210120002]
- European Union's Horizon 2020 research and innovation program [871124]
- China Scholarship Council [20180844036]
- European Research Council (ERC) [683024] Funding Source: European Research Council (ERC)
- Agence Nationale de la Recherche (ANR) [ANR-19-CE29-0008] Funding Source: Agence Nationale de la Recherche (ANR)
The study focuses on a multi-responsive molecular switch that can be controlled by light and acid-base equilibrium to modulate its properties and functions.
Multi-responsive functional molecules are key for obtaining user-defined control of the properties and functions of chemical and biological systems. In this respect, pH-responsive photochromes, whose switching can be directed with light and acid-base equilibria, have emerged as highly attractive molecular units. The challenge in their design comes from the need to accommodate application-defined boundary conditions for both light- and protonation-responsivity. Here we combine time-resolved spectroscopic studies, on time scales ranging from femtoseconds to seconds, with density functional theory (DFT) calculations to elucidate and apply the acidochromism of a recently designed iminothioindoxyl (ITI) photoswitch. We show that protonation of the thermally stable Z isomer leads to a strong batochromically-shifted absorption band, allowing for fast isomerization to the metastable E isomer with light in the 500-600 nm region. Theoretical studies of the reaction mechanism reveal the crucial role of the acid-base equilibrium which controls the populations of the protonated and neutral forms of the E isomer. Since the former is thermally stable, while the latter re-isomerizes on a millisecond time scale, we are able to modulate the half-life of ITIs over three orders of magnitude by shifting this equilibrium. Finally, stable bidirectional switching of protonated ITI with green and red light is demonstrated with a half-life in the range of tens of seconds. Altogether, we designed a new type of multi-responsive molecular switch in which protonation red-shifts the activation wavelength by over 100 nm and enables efficient tuning of the half-life in the millisecond-second range.
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