Crystallographic analysis reveals varying bond lengths in In(II)-In(II) complexes, highlighting the flexibility of the mausolate coordination environment.
The voluminous rigid cage of the mausolate ligand [1]2- is capable of strongly binding the largest cations in the periodic table. The high rigidity and capacity of the mausolate also makes it capable of sequestering two In(II) cations, forcing them together to produce an In(II)-In(II) bond up to 76 pm shorter than any previously reported. Through crystallographic analysis of fifteen such structures, we find this bond length can vary depending on the counterion by up to 90 pm. This binding behavior extends to the Ga(II)-Ga(II) analogue and mixed In(II)-Ga(II) complexes. The unusual and adaptable coordination environment of the mausolate suggests enormous potential for the encapsulation of not only single radiometal cations but also new heterometal complexes where it acts as a bridging ligand of unprecedented geometry.
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Smart et al. (2025) studied this question.
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