Luminescent Cationic Group 4 Metallocene Complexes Stabilized by Pendant N-Donor Groups

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F21%3A00542202" target="_blank" >RIV/61388955:_____/21:00542202 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388980:_____/21:00542202 RIV/00216208:11310/21:10428560

Výsledek na webu

<a href="http://hdl.handle.net/11104/0319998" target="_blank" >http://hdl.handle.net/11104/0319998</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.1c00461" target="_blank" >10.1021/acs.inorgchem.1c00461</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Luminescent Cationic Group 4 Metallocene Complexes Stabilized by Pendant N-Donor Groups

Popis výsledku v původním jazyce

Cationic group 4 metallocene complexes with pendant imine and pyridine donor groups were prepared as stable crystalline [B(C6F5)4]− salts either by protonation of the intramolecularly bound ketimide moiety in neutral complexes [(η5-C5Me5){η5-C5H4CMe2CMe2C(R)═N-κN}MCl] (M = Ti, Zr, Hf, R = t-Bu, Ph) by PhNMe2H+[B(C6F5)4]− to give [(η5-C5Me5){η5-C5H4CMe2CMe2C(R)═NH-κN}MCl]+[B(C6F5)4]− or by chloride ligand abstraction from the complexes [(η5-C5Me5)(η5-C5H4CMe2CH2C5H4N)MCl2] (M = Ti, Zr) by Li[B(C6F5)4]·2.5Et2O to give [(η5-C5Me5)(η5-C5H4CMe2CH2C5H4N-κN)MCl]+[B(C6F5)4]−. Solid state structures of the new compounds were established by X-ray diffraction analysis, and their electrochemical behavior was studied by cyclic voltammetry. The cationic complexes of Zr and Hf, compared to the corresponding neutral species, exhibited significantly enhanced luminescence predominantly from triplet ligand-to-metal (3LMCT) excited states with lifetimes up to 62 μs and quantum yields up to 58% in the solid state. DFT calculations were performed to explain the structural features and optical and electrochemical properties of the complexes.

Název v anglickém jazyce

Luminescent Cationic Group 4 Metallocene Complexes Stabilized by Pendant N-Donor Groups

Popis výsledku anglicky

Cationic group 4 metallocene complexes with pendant imine and pyridine donor groups were prepared as stable crystalline [B(C6F5)4]− salts either by protonation of the intramolecularly bound ketimide moiety in neutral complexes [(η5-C5Me5){η5-C5H4CMe2CMe2C(R)═N-κN}MCl] (M = Ti, Zr, Hf, R = t-Bu, Ph) by PhNMe2H+[B(C6F5)4]− to give [(η5-C5Me5){η5-C5H4CMe2CMe2C(R)═NH-κN}MCl]+[B(C6F5)4]− or by chloride ligand abstraction from the complexes [(η5-C5Me5)(η5-C5H4CMe2CH2C5H4N)MCl2] (M = Ti, Zr) by Li[B(C6F5)4]·2.5Et2O to give [(η5-C5Me5)(η5-C5H4CMe2CH2C5H4N-κN)MCl]+[B(C6F5)4]−. Solid state structures of the new compounds were established by X-ray diffraction analysis, and their electrochemical behavior was studied by cyclic voltammetry. The cationic complexes of Zr and Hf, compared to the corresponding neutral species, exhibited significantly enhanced luminescence predominantly from triplet ligand-to-metal (3LMCT) excited states with lifetimes up to 62 μs and quantum yields up to 58% in the solid state. DFT calculations were performed to explain the structural features and optical and electrochemical properties of the complexes.

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

2021

Kód důvěrnosti údajů

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

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

1520-510X

Svazek periodika

60

Číslo periodika v rámci svazku

10

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

14

Strana od-do

7315-7328

Kód UT WoS článku

000653539100054

EID výsledku v databázi Scopus

2-s2.0-85106382164