RE4[P1–x(C2)x]3 (RE = La–Nd): the Mixed Anionic Substructure Formed by Phosphorus and Carbon

The rare‐earth phosphide carbides RE₄P_1–x(C₂)_x]₃ (RE = La, Ce, Pr, Nd) represent the first example of a mixed anionic substructure formed by phosphorus and carbon, being the first step toward the formation of the mixed inorganic P–C species. The peculiarities of the crystal structure, magnetic properties, XAS data, and quantum chemical calculation results confirm the ionic nature of the interaction between the rare‐earth cations RE and phosphorus anions, while complex interaction of π states of the C₂ anions and d (and/or f) states of the RE components is indicated. Thus, despite the extensive chemical analogy between the phosphide carbides and phosphide silicides, the atomic interactions stabilizing the structural motif are slightly different.