Luminescent Zirconocene Complexes with Pendant Phosphine Chalcogenide Donor Groups

0571054 - ÚFCH JH 2024 RIV US eng J - Článek v odborném periodiku
Urbán, Béla - Dunlop, David - Gyepes, R. - Kubát, Pavel - Lang, Kamil - Horáček, Michal - Pinkas, Jiří - Šimková, Ludmila - Lamač, Martin
Luminescent Zirconocene Complexes with Pendant Phosphine Chalcogenide Donor Groups.
Organometallics. Roč. 42, č. 12 (2023), s. 1373-1385. ISSN 0276-7333. E-ISSN 1520-6041
Grant CEP: GA ČR(CZ) GA19-00204S
Institucionální podpora: RVO:61388955 ; RVO:61388980
Klíčová slova: zirconocene complexes * ligand to metal charge transfer * luminiscence
Obor OECD: Physical chemistry; Inorganic and nuclear chemistry (UACH-T)
Impakt faktor: 2.8, rok: 2022
Způsob publikování: Open access

Neutral zirconocene complexes of the type [(η5-C5Me5){η5-C5H4CMe2P(═E)Ph2}ZrCl2] (E = not present, O, S, or Se) with a cyclopentadienyl-attached phosphine and related phosphine oxide, sulfide, or selenide moiety were prepared and converted to their cationic counterparts by chloride abstraction with K[B(C6F5)4] to give compounds of the general formula [(η5-C5Me5){η5-C5H4CMe2P(═E)Ph2-κE}ZrCl]+[B(C6F5)4]−. Alternatively, the chloride abstraction was accomplished by the reaction with ZnCl2 to give the same cationic species with a [Zn2Cl6]2– counteranion. The ionic complexes, unlike the neutral counterparts, exhibited strongly enhanced luminescence properties originating in triplet ligand-to-metal (3LMCT) excited states. Luminescence quantum yields up to 0.95 were determined in the solid state with luminescence lifetimes up to 50.6 μs. In addition to structural characterization of the prepared complexes by X-ray diffraction methods, their electrochemistry was investigated by cyclic voltammetry, and their photophysical properties were studied with quantum-chemical calculations.
Trvalý link: https://hdl.handle.net/11104/0342364