Chemistry-Inspired Adaptable Framework Structures

Adaptable crystalline frameworks are important in modern solid-state chemistry as they are able to accommodate a wide range of elements, oxidation states, and stoichiometries. Owing to this ability, such adaptable framework structures are emerging as the prototypes for technologically important advanced functional materials. In this Account, the idea of cosubstitution is explored as a useful "pairing" concept that can potentially lead to the creation of many new members of one particular framework structure. Cosubstitution as practiced is the simultaneous replacement of two or more cations, anions, complex anions, other fundamental building units, or vacancies. Although the overall sum of the oxidation states is constant, each component is not necessarily isovalent. This methodology is typically inspired by either mineral-type structural prototypes found in nature or those discovered in the laboratory. Either path leads to the appearance of new phases and the discovery of new materials. In addition, the chemical cosubstitution approach can be successfully adopted to improve physical properties associated with structures. This Account is structured as follows: first, we illustrate the significance and background of chemical cosubstitution by reviewing mineral-inspired structures, such as perovskite and lyonsite, and the structural unit discovered in some selected solid state compounds. With time, the number of lyonsite related phases should rival or even surpass the perovskite family. Several members of the lyonsite-type have been identified as Li-ion conductors and photocatalysts. There is also a noncentrosymmetric structure-type, and therefore the other properties associated with the loss of inversion symmetry should be anticipated. Next, we illustrate recent advances in the synthesis of the new cosubstituted solid state materials from our two groups including (1) nonlinear optical materials, (2) luminescent materials, (3) transparent conducting oxides, and (4) photocatalyst and photovoltaic materials. We emphasize that a concerted and rigorous theoretical and experimental approach will be required to define thermodynamic stability of the complex cosubstitution chemistries, structures, and properties that are yet unknown. We conclude by summarizing the topic and suggesting other possible adaptable framework structures where cosubstitution can be expected.