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Dual Fluorescence and Phosphorescence Emissions from Dye-Modified (NCN)-Bismuth Pincer Thiolate Complexes

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2024

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Inorganic Chemistry. American Chemical Society (ACS). 2024, 63(32), S. 14876-14888. ISSN 0020-1669. eISSN 1520-510X. Verfügbar unter: doi: 10.1021/acs.inorgchem.4c01023

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We report the synthesis, characterization, and photophysical properties of four new dye-modified (NCN)Bi pincer complexes with two mercaptocoumarin or mercaptopyrene ligands. Their photophysical properties were probed by UV/vis spectroscopy, photoluminescence (PL) studies, and time-dependent density functional theory (TD-DFT) calculations. Absorption spectra of the complexes are dominated by mixed pyrene or coumarin π → π*/n(pS) → pyrene or coumarin π* transitions. While unstable toward reductive elimination of the corresponding disulfide under irradiation at room temperature, the complexes provide stable emissions at 77 K. Under these conditions, coumarin complexes 2 and 4 exhibit exclusively green phosphorescence at 508 nm. In contrast, the emissive properties of pyrene complexes 1 and 3 depend on the excitation wavelength and on sample concentration. Irradiation into the lowest-energy absorption band exclusively triggers red phosphorescence from the pyrenyl residues at 640 nm. At concentrations c < 1 μM, excitation into higher excited electronic states results in blue pyrene fluorescence. With increasing c (1–100 μM), the emission profile changes to dual fluorescence and phosphorescence emission, with a steady increase of the phosphorescence intensity, until at c ≥ 1 mM only red phosphorescence ensues. Progressive red-shifts and broadening of steady-state excitation spectra with increasing sample concentration suggest the presence of static excimers, as we observe it for concentrated solutions of pyrene. Crystalline and powdered samples of 1 indeed show intermolecular association through π-stacking. TD-DFT calculations on model dimers and a tetramer of 1 support the idea of aggregation-induced intersystem crossing (AI-ISC) as the underlying reason for this behavior.

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540 Chemie

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Aromatic Compounds, Hydrocarbons, Ligands, Oligomers, Phosphorescence

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ISO 690GEPPERT, Marcel, Kai JELLINEK, Michael LINSEIS, Michael BODENSTEINER, Jessica GEPPERT, Miriam M. UNTERLASS, Rainer F. WINTER, 2024. Dual Fluorescence and Phosphorescence Emissions from Dye-Modified (NCN)-Bismuth Pincer Thiolate Complexes. In: Inorganic Chemistry. American Chemical Society (ACS). 2024, 63(32), S. 14876-14888. ISSN 0020-1669. eISSN 1520-510X. Verfügbar unter: doi: 10.1021/acs.inorgchem.4c01023
BibTex
@article{Geppert2024-08-12Fluor-70535,
  year={2024},
  doi={10.1021/acs.inorgchem.4c01023},
  title={Dual Fluorescence and Phosphorescence Emissions from Dye-Modified (NCN)-Bismuth Pincer Thiolate Complexes},
  number={32},
  volume={63},
  issn={0020-1669},
  journal={Inorganic Chemistry},
  pages={14876--14888},
  author={Geppert, Marcel and Jellinek, Kai and Linseis, Michael and Bodensteiner, Michael and Geppert, Jessica and Unterlass, Miriam M. and Winter, Rainer F.}
}
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