Closed-to-open-shell ground state photoswitching of thienyl-based acylhydrazones

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00635592" target="_blank" >RIV/61388963:_____/25:00635592 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22310/25:43931522 RIV/61989100:27740/25:10257983

Výsledek na webu

<a href="https://doi.org/10.1039/D5TC00826C" target="_blank" >https://doi.org/10.1039/D5TC00826C</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d5tc00826c" target="_blank" >10.1039/d5tc00826c</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Closed-to-open-shell ground state photoswitching of thienyl-based acylhydrazones

Popis výsledku v původním jazyce

Photoswitches convert a photon to molecular information through a reversible change in bonding or configuration. Applications of photoswitches are determined by their different properties in the two states, spanning from catalysis, to allosteric activation, to photopharmacology, up to materials and devices such as memories that can store optical information in chemical bonds. For the latter, operation in the solid state and different means to read/write/erase the information must be possible. These features, however, are challenging to achieve due to close molecular packing and intermolecular interactions. Here, we present acylhydrazones that photoswitch even in the solid state and adopt an open-shell triplet ground state electronic configuration in the photoswitched form, which is very long-lived. The optically stored information can thus be read magnetically and completely erased by applying an electrochemical potential. In addition, ab initio calculations identified the closed-to-open-shell pathway and explained the singlet-triplet crossing. Photoswitching of the closed/open-shell ground state electronic structure is a fundamentally new feature, which can bring new opportunities and applications. We demonstrate it in an example of the open-shell state of the photoswitch used as an initiator of radical benzylic bromination and radical debromination of an aromatic ring. However, the presented phenomenon is robust and insensitive to conditions, thus showing potential in a broad range from heterogeneous catalysis to spintronics.

Název v anglickém jazyce

Closed-to-open-shell ground state photoswitching of thienyl-based acylhydrazones

Popis výsledku anglicky

Photoswitches convert a photon to molecular information through a reversible change in bonding or configuration. Applications of photoswitches are determined by their different properties in the two states, spanning from catalysis, to allosteric activation, to photopharmacology, up to materials and devices such as memories that can store optical information in chemical bonds. For the latter, operation in the solid state and different means to read/write/erase the information must be possible. These features, however, are challenging to achieve due to close molecular packing and intermolecular interactions. Here, we present acylhydrazones that photoswitch even in the solid state and adopt an open-shell triplet ground state electronic configuration in the photoswitched form, which is very long-lived. The optically stored information can thus be read magnetically and completely erased by applying an electrochemical potential. In addition, ab initio calculations identified the closed-to-open-shell pathway and explained the singlet-triplet crossing. Photoswitching of the closed/open-shell ground state electronic structure is a fundamentally new feature, which can bring new opportunities and applications. We demonstrate it in an example of the open-shell state of the photoswitch used as an initiator of radical benzylic bromination and radical debromination of an aromatic ring. However, the presented phenomenon is robust and insensitive to conditions, thus showing potential in a broad range from heterogeneous catalysis to spintronics.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GM22-11299M" target="_blank" >GM22-11299M: Reakční sítě na fázových rozhraních pro dynamickou samoskladbu</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

Journal of Materials Chemistry C

ISSN

2050-7526

e-ISSN

2050-7534

Svazek periodika

13

Číslo periodika v rámci svazku

19

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

7

Strana od-do

9520-9526

Kód UT WoS článku

001468674200001

EID výsledku v databázi Scopus

2-s2.0-105003027182