Nine single crystal X-ray structures of the LnIIINa(OAc)4[12-MCMnIII(N)shi-4](H2O)4�6DMF complex, where �OAc is acetate, shi3- is salicylhydroximate, DMF is N,N-dimethylformamide, and LnIII is PrIII, NdIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, and YbIII will be presented. These complexes demonstrate the first inclusion of LnIII ions into the 12-MC-4 framework. The X-ray structures reveal that the identity of the LnIII ion affects the structural 12-MCMnIII(N)shi-4 framework. The largest LnIII in terms of ionic radius, PrIII, causes an expansion of the 12-MCMnIII(N)shi-4 framework as evident in longer cross cavity MnIII � MnIII distances, cross cavity oxime oxygen � oxygen distances, and average adjacent MnIII � MnIII distances. Thus, the PrIIINa(OAc)4[12-MCMnIII(N)shi-4](H2O)4�6DMF complex has the largest metallacrown cavity. In addition, the PrIII causes the 12-MCMnIII(N)shi-4 framework to be the most bowled as evident in the largest bond angles about the axial coordination of the ring MnIII ions and the greatest distance difference of the LnIIIbetween the oxime oxygen mean plane and the manganese mean plane.

Novel lanthanide-containing 12-MC-4 complexes

247th National Meeting (2014)

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