Perovskite oxyhydrides have attracted recent attention due to their intriguing properties such as ionic conductivity and catalysis, but their repertoire is still restricted compared to perovskite oxynitrides and oxyfluorides. Historically, perovskite oxyhydrides have been prepared mostly by topochemical reactions and high-pressure (HP) reactions, while in this study, we employed a mechanochemical (MC) approach, which enables the synthesis of a series of ABO2H-type oxyhydrides, including those with the tolerance factor (t) much smaller than 1 (e.g., SrScO2H with t = 0.936) which cannot be obtained by HP synthesis. The octahedral tilting, often present in perovskite oxides, does not occur, suggesting that the lack of π-symmetry of the H 1s orbital and the large polarization destabilize tilted low-symmetry structures. Interestingly, SrCrO2H (t = 0.997), previously reported with the HP method, was not achieved with the MC method. A comparative analysis revealed a correlation between the feasibility of MC reactions and the (calculated) shear modulus of the starting reagents (binary oxides and hydrides). Notably, this indicator is not exclusive to oxyhydride perovskites but extends to oxide perovskites (SrMO3). This study demonstrates that MC synthesis offers unique opportunities not only to expand the compositional space in oxyhydrides in various structural types but also to provide a guide for the choice of starting materials for the synthesis of other compounds.
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