One-dimensional iodine-rich iodobismuthates(III), Cat{[BiI](I)} [Cat = 1,4-MePy () and 1-EtBMAP ()], feature the highest amount of "trapped" diiodine units in polyhalogen-halometalates of p-block elements. Both complexes have narrow optical band gaps (1.55 and 1.63 eV, respectively) and moderate thermal stability.
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