Narrowing the tolerance factor limits for hybrid organic-inorganic dicyanamide-perovskites
Javier García‐Ben, Alberto García‐Fernández, Pedro Dafonte-Rodríguez, Ignacio Delgado-Ferreiro, Ute B. Cappel, Socorro Castro‐García, Manuel Sánchez‐Andújar, Juan Manuel Bermúdez‐García, M. A. Señarís‐Rodríguez
Abstract
In this work we focus in setting the limits of the tolerance factor and the size of the A-cations that stabilize the perovskite structure in hybrid dicyanamide compounds [A][Mn(dca)3]. For this purpose, we propose an alternative, simple approach to calculate a more realistic effective ionic radius for the large and anisotropic A-cations often present in these type of compounds. We test the proposed procedure by analysing the crystal structures of [A][Mn(dca)3] dicyanamide hybrids reported in the literature and recalculating the tolerance factors of such compounds, as well as by preparing five new [A][Mn(dca)3] members, discussing also the influence of the A-cation shape in the stability limits of the perovskite structure. Interestingly, such methodology is not only useful to develop new compounds of the emerging family of (multi)functional multi(stimuli)-responsive dicyanamide materials but can also be applied to other hybrid organic-inorganic perovskites and related materials.