Bismuth Iodide Hybrid Organic‐Inorganic Crystal Structures and Utilization in Formation of Textured BiI 3 Film

Two new and one redetermination of metastable bismuth iodide hybrid organic‐inorganic structure incorporating the solvents 2,3,4,5‐tetrahydrothiophene 1,1‐dioxide Bi 2 I 6 · (C 4 H 8 O 2 S) 2 ( 1 ), N , N ‐dimethylmethanamide Bi 3 I 12 · Bi(C 3 H 7 NO) 8 ( 2 ), and dimethyl sulfoxide Bi 2 I 9 · Bi(C 2 H 6 OS) 8 ( 3 ), are reported. In these compounds the size and shape of the inorganic moiety can be selectively adjusted by choice of solvent, which takes the form of infinite neutral linear BiI 3 chains in 1 and isolated Bi–I clusters [Bi 3 I 12 ] 3– in 2 . The crystals are short‐lived and decompose to form BiI 3 under ambient conditions. Highly textured BiI 3 films can be fabricated by spin coating, which is shown for the case of 3 .