Conformational Locking of the Geometry in Photoluminescent Cyclometalated N^C^N Ni(II) Complexes DOI Creative Commons
Maryam Niazi, Iván Maisuls,

Anne Lukas

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(9), P. 1901 - 1901

Published: April 24, 2025

In our research aimed at replacing precious transition metals like platinum with abundant base such as nickel for efficient triplet emitters, we synthesized and studied Ni(II) complexes [Ni(LNHR)Cl]. These containing the N^C^N cyclometalating dipyridyl-phenide ligand, equipped pending H-bonding amine groups (NH(C₆H₅) (LNHPh) NH(C₆H₅CH₂), ClLNHBn). Molecular structures determined from experimental X-ray diffractometry density functional theory (DFT) calculations in ground state showed marked deviation of Cl− coligand (ancillary ligand) ideal planar coordination, τ4 values 0.35 0.33, respectively, along hydrogen bonding interactions ligand NH function coligand. The exhibit long-wavelength absorption bands approximately 425 nm solution, spectra being accurately reproduced through time-dependent (TD-DFT) calculations. Vibrationally structured emission profiles steady-state photoluminescence quantum yields 30% [Ni(LNHPh)Cl] 40% [Ni(LNHBn)Cl] (along dual excited lifetimes ns ms range) were found frozen 2-methyl-tetrahydrofuran (2MeTHF) glassy matrices 77 K. Furthermore, within a poly(methyl methacrylate) matrix, centered around 550 temperature range 6 K to 300 similar Based on TD-DFT potential scans metal–ligand (Ni–N) coordinate, that rigid environment restricts geometry Franck-Condon region, either T5 or singlet S4 could contribute photoluminescence.

Language: Английский

Pt(II), Pd(II), and Ni(II) Complexes with Tridentate Cyclometalating Five- and Six-Ring Chelating N^C*N, C^N*N, and N*C*N Quinolinyl Ligands DOI
Leo Payen, Tobias Lapić, Mathias S. Wickleder

et al.

Organometallics, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

Language: Английский

Citations

0
Synthesis and Photophysics of the Doubly Cyclometalated Pd(II) Complexes [Pd(C∧N∧C)(L)], L = PPh3, AsPh3, and SbPh3 DOI
Rose Jordan,

Sam Kler,

Iván Maisuls

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

While Pt(II) complexes containing doubly cyclometalated ligands as tridentate luminophores are well studied, the synthetic accessibility of their Pd(II) counterparts was lacking for a long time. Inspired by recent report on synthesis [Pd(dpp)(PPh3)] involving C∧N∧C coordination mode (with dpp2– = 2,6-di(phenid-2-yl)pyridine) and following our own work closely related Pt(II)-based compounds, we produced series [Pd(dpp)(PnPh3)] (Pn P, As, Sb) optimizing procedure exploring reactivity in process. Our study electrochemical (cyclic voltammetry) photophysical (UV–vis absorption emission, transient (TA) spectroscopy) properties Pd(C∧N∧C) represents first characterization. We observed UV–vis bands down to 450 nm HOMO–LUMO gaps around 3.2 V, which show minimal variation with different PnPh3 coligands. A more pronounced influence coligand time-resolved emission TA spectroscopy. The highest photoluminescence quantum yield (ΦL) found [Pd(dpp)(AsPh3)], reaching 0.06. interpretation spectroscopic data is supported (TD-)DFT calculations. Additionally, structural several dinuclear complexes, including precursor {[Pd(dppH)(μ-Cl)]}2 multiple decomposition products sensitive compounds [Pd(dpp)(PnPh3)].

Language: Английский

Citations

0
Conformational Locking of the Geometry in Photoluminescent Cyclometalated N^C^N Ni(II) Complexes DOI Creative Commons
Maryam Niazi, Iván Maisuls,

Anne Lukas

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(9), P. 1901 - 1901

Published: April 24, 2025

In our research aimed at replacing precious transition metals like platinum with abundant base such as nickel for efficient triplet emitters, we synthesized and studied Ni(II) complexes [Ni(LNHR)Cl]. These containing the N^C^N cyclometalating dipyridyl-phenide ligand, equipped pending H-bonding amine groups (NH(C₆H₅) (LNHPh) NH(C₆H₅CH₂), ClLNHBn). Molecular structures determined from experimental X-ray diffractometry density functional theory (DFT) calculations in ground state showed marked deviation of Cl− coligand (ancillary ligand) ideal planar coordination, τ4 values 0.35 0.33, respectively, along hydrogen bonding interactions ligand NH function coligand. The exhibit long-wavelength absorption bands approximately 425 nm solution, spectra being accurately reproduced through time-dependent (TD-DFT) calculations. Vibrationally structured emission profiles steady-state photoluminescence quantum yields 30% [Ni(LNHPh)Cl] 40% [Ni(LNHBn)Cl] (along dual excited lifetimes ns ms range) were found frozen 2-methyl-tetrahydrofuran (2MeTHF) glassy matrices 77 K. Furthermore, within a poly(methyl methacrylate) matrix, centered around 550 temperature range 6 K to 300 similar Based on TD-DFT potential scans metal–ligand (Ni–N) coordinate, that rigid environment restricts geometry Franck-Condon region, either T5 or singlet S4 could contribute photoluminescence.

Language: Английский

Citations

0