Luminescent Zirconocene Complexes with Pendant Phosphine Chalcogenide Donor Groups

0571054 - ÚFCH JH 2024 RIV US eng J - Journal Article
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
R&D Projects: GA ČR(CZ) GA19-00204S
Institutional support: RVO:61388955 ; RVO:61388980
Keywords : zirconocene complexes * ligand to metal charge transfer * luminiscence
OECD category: Physical chemistry; Inorganic and nuclear chemistry (UACH-T)
Impact factor: 2.8, year: 2022
Method of publishing: 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.
Permanent Link: https://hdl.handle.net/11104/0342364