The Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth ComplexesThe Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth Complexes.

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 671 to 20 µs. 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.