Deuter, Katharina L. and Kather, Felix and Linseis, Michael and Bodensteiner, Michael and Winter, Rainer F. (2025) The Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth Complexes. CHEMISTRY-A EUROPEAN JOURNAL, 31 (6). ISSN 0947-6539, 1521-3765
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We present a series of six hypervalent bismuth complexes Bi(R1PDPR2)X bearing ligands characterized by the pyridine-2,6-bis(pyrrolide) (PDP) structural motif. While bismuth holds considerable potential for facilitating efficient intersystem crossing (ISC), reports on phosphorescent molecular bismuth complexes are still scarce and mostly based on systems that exhibit inter- or intraligand charge transfer character of their optical excitations. Herein, the UV/vis absorptive, luminescent, and electrochemical properties of complexes Bi(R1PDPR2)X are explored, where the substituents R1 and R2, as well as the halide ligand X are varied. These compounds are characterized by an intense HOMO -> LUMO transition of mixed ligand-to-metal charge transfer (LMCT) and interligand charge transfer (LL'CT) character, as shown by time-dependent density functional theory (TD-DFT) calculations. At 77 K in a 2-MeTHF matrix, these compounds exhibit red, long-lived phosphorescence with lifetimes ranging from 479 to 14 mu s. Cyclic voltammetry measurements and TD-DFT calculations show that the substituents influence HOMO and LUMO energies to almost equal extent, resulting in nearly constant emission wavelengths throughout this series. Single-crystal X-ray diffraction studies of four of the six complexes exemplify the inherent Lewis acidity of the coordinated Bi3+ ion, in spite of its hypervalency.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MAIN-GROUP ELEMENTS; PHOTOREDOX CATALYSIS; LIGHT; PHOSPHORESCENCE; CHEMISTRY; COORDINATION; ANTIMONY; Bismuth complexes; Phosphorescence; X-ray crystallography; TD-DFT calculations |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Central Analytical Services |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 17 Mar 2026 09:47 |
| Last Modified: | 17 Mar 2026 09:47 |
| URI: | https://pred.uni-regensburg.de/id/eprint/64548 |
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