Materials with low dimensionality have been identified as potential candidates for electronic and optoelectronic applications. Semiconducting polyphosphides with one‐dimensional (1D) substructures, such as materials adopting the HgPbP 14 ‐structure type or Pb 5 I 2 P 28 , are examples of this class. Herein, we report on (PbBr 2 )Pb 2 P 14 2 that crystallizes monoclinically, in space group P 2 1 / n (No. 14), with the cell parameters a = 9.8175(7) Å, b = 17.5841(11) Å, c = 18.9568(15) Å, and β = 97.612(6)°. The title compound consists of formal charge‐neutral PbBr 2 units that interlink entities, resulting in a more descriptive formula (PbBr 2 )Pb 2 P 14 2 rather than the sum formula Pb 5 Br 2 P 28 . Raman spectroscopy was used to support this adduct description, indicating that the title compound exhibits a bonding situation within the Pb substructure similar to PbBr 2 . First‐principle density functional theory (DFT) calculations on (PbBr 2 )Pb 2 P 14 2 and isostructural (PbI 2 )Pb 2 P 14 2 (Pb 5 I 2 P 28 ) illustrate typical semiconductor behavior for these two polyphosphides. Photoluminescence spectroscopy shows two band gaps at 1.90 and 1.79 eV in both (PbBr 2 )Pb 2 P 14 2 and (PbI 2 )Pb 2 P 14 2 , which align with the calculated values found from DFT calculations.
Vosseler et al. (Thu,) studied this question.