Group 4 metallocene derivatives as a new class of singlet oxygen photosensitizers

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F22%3A00547509" target="_blank" >RIV/61388955:_____/22:00547509 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388980:_____/22:00547509

Výsledek na webu

<a href="http://hdl.handle.net/11104/0323721" target="_blank" >http://hdl.handle.net/11104/0323721</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.jphotochem.2021.113619" target="_blank" >10.1016/j.jphotochem.2021.113619</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Group 4 metallocene derivatives as a new class of singlet oxygen photosensitizers

Popis výsledku v původním jazyce

Photosensitizers, which produce singlet oxygen O2(1Δg) under light irradiation, have attracted much attention due to their application potential in medicine and material science. In this respect, we recently reported on cationic metallocene complexes with pendant N-donor moieties, which exhibited enhanced luminescence in the solid-state originating from their triplet states with luminescence quantum yields, ΦL, up to approximately 0.52, unprecedented for this class of compounds. This finding suggested that these complexes can be efficient singlet oxygen photosensitizers. Herein, we evaluate the photogeneration of O2(1Δg) by several Ti, Zr and Hf metallocenes in dichloromethane solution, including recently described cationic derivatives. After excitation by UV A light, cationic Zr and Hf metallocenes stabilized by N-donor imine and pyridine moieties exhibited green, yellow or orange luminescence from long-lived 3LMCT excited states (ΦL ∼ 0.02 – 0.40 in argon-saturated solutions) and efficient O2(1Δg) production (ΦΔ ∼ 0.29 – 0.77 in air-saturated solutions). In contrast, parent neutral Zr complexes and cationic Ti derivatives with enhanced absorption of visible light, exhibited lesser ability to produce O2(1Δg) (ΦΔ < 0.10), similar to Zr and Ti metallocene dihalogenides. The experimentally established spectroscopic and photophysical behavior was probed computationally at the TD-DFT level.

Název v anglickém jazyce

Group 4 metallocene derivatives as a new class of singlet oxygen photosensitizers

Popis výsledku anglicky

Photosensitizers, which produce singlet oxygen O2(1Δg) under light irradiation, have attracted much attention due to their application potential in medicine and material science. In this respect, we recently reported on cationic metallocene complexes with pendant N-donor moieties, which exhibited enhanced luminescence in the solid-state originating from their triplet states with luminescence quantum yields, ΦL, up to approximately 0.52, unprecedented for this class of compounds. This finding suggested that these complexes can be efficient singlet oxygen photosensitizers. Herein, we evaluate the photogeneration of O2(1Δg) by several Ti, Zr and Hf metallocenes in dichloromethane solution, including recently described cationic derivatives. After excitation by UV A light, cationic Zr and Hf metallocenes stabilized by N-donor imine and pyridine moieties exhibited green, yellow or orange luminescence from long-lived 3LMCT excited states (ΦL ∼ 0.02 – 0.40 in argon-saturated solutions) and efficient O2(1Δg) production (ΦΔ ∼ 0.29 – 0.77 in air-saturated solutions). In contrast, parent neutral Zr complexes and cationic Ti derivatives with enhanced absorption of visible light, exhibited lesser ability to produce O2(1Δg) (ΦΔ < 0.10), similar to Zr and Ti metallocene dihalogenides. The experimentally established spectroscopic and photophysical behavior was probed computationally at the TD-DFT level.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA19-00204S" target="_blank" >GA19-00204S: Komplexy elektronově deficitních přechodných kovů s luminiscenčními vlastnostmi</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

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

Název periodika

Journal of Photochemistry and Photobiology A-Chemistry

ISSN

1010-6030

e-ISSN

1873-2666

Svazek periodika

424

Číslo periodika v rámci svazku

FEB 2022

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

10

Strana od-do

113619

Kód UT WoS článku

000718451600004

EID výsledku v databázi Scopus

2-s2.0-85118508141