We report the synthesis, X-ray structure, and solution behavior of a "nanosquare" formed by four repeating ( i Pr 2 BiI) units. The title complex [ i Pr 2 BiI] 4 (1) formed spontaneously as the major product from the reaction of i Pr 3 Bi with MI 2 (M = Mn, Co, Fe). Complex 1 was then more directly synthesized via bromination of i Pr 3 Bi to form ( i Pr 2 BiBr), followed by iodide substitution. The X-ray structure of 1 exhibited acute Bi−I−Bi bonds (∼85−95°) that enabled formation of the hollow square motif. Synthetic control experiments with R 2 BiX (R = i Pr, Bn; X = I, Br) revealed that the identities of both the halide and bismuth R group are determinants for square formation: the bromo-substituted [ i Pr 2 BiBr] n (2) and benzyl-substituted [Bn 2 BiI] n (3) variants formed only polymers as determined by X-ray crystallography. Density functional theory calculations revealed nearly pure porbital-based bonding molecular orbitals on both iodide and bismuth, facilitating the ∼90°/180°bonding motifs.
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