Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15640%2F21%3A73607355" target="_blank" >RIV/61989592:15640/21:73607355 - isvavai.cz</a>

Result on the web

<a href="https://pubs.rsc.org/en/content/articlelanding/2021/SC/D0SC07000A" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2021/SC/D0SC07000A</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d0sc07000a" target="_blank" >10.1039/d0sc07000a</a>

Result language

angličtina

Original language name

Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

21001 - Nano-materials (production and properties)

Project

<a href="/en/project/EF16_019%2F0000754" target="_blank" >EF16_019/0000754: Nanotechnologies for Future</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2021

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Chemical Science

ISSN

2041-6520

e-ISSN

—

Volume of the periodical

2021

Issue of the periodical within the volume

12

Country of publishing house

GB - UNITED KINGDOM

Number of pages

11

Pages from-to

4588-4598

UT code for WoS article

000635768300038

EID of the result in the Scopus database

2-s2.0-85103688959