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Wustrow, A., McDermott, M. J., O'Nolan, D., Liu, C.-H., Tran, G. T., McBride, B. C., Vornholt, S. M., Feng, C., Dwaraknath, S. S., Chapman, K. W., Billinge, S. J. L., Sun, W., Persson, K. A., & Neilson, J. R. (2022). Reaction selectivity in cometathesis: Yttrium manganese oxides. Chemistry of Materials, 34(10), 4694-4702. https://doi.org/10.1021/acs.chemmater.2c00636
Synthesis of metastable materials by control of reaction pathways is facilitated by low-temperature routes. Cometathesis reactions have recently been shown to lower reaction temperatures when compared to single-ion metathesis reactions. Here, we share the discovery of how and why different precursor combinations radically change the reaction pathway and selectively yield different product polymorphs. By studying reactions of the general form, xAyMnO2 + (1 - x) A ' zMnO2 + YOCl -> YMnO3 + xAyCl + (1 - x)A ' zCl (A and A ' = Li, Na, Mg, and Ca, y and z = 1/2 or 1, and 0