Figure 1.

Fragment‐based searching for phosphorus allotropes. a) Schematic overview of the approach. The 1D tubes in fibrous phosphorus,6 described by the [P9]P2[P8]P2 repeat unit, can be decomposed in two different ways: either based on an automated algorithm as in Ref. 22, or on conventions in the chemical literature. These fragments are then used as input for GAP‐RSS searches. b,c) Example results that structurally resemble Hittorf's phosphorus,1 but are composed of only one type of cage, either the cross‐linked P9]P2 or the non‐linked P8]P2 unit. d) Statistics from a large‐scale search, with 100 000 attempts per type of seed fragment. The bars give the number of successful attempts (including duplicates), either including or excluding small‐ring structures, for each type of fragment with which the search was seeded. Structural drawings were created using VESTA.24