Narrowing the tolerance factor limits for hybrid organic-inorganic dicyanamide-perovskites

• Published in: Journal of solid state chemistry 2022-12, Vol.316, p.123635, Article 123635
• Main Authors: García-Ben, Javier, García-Fernández, Alberto, Dafonte-Rodríguez, Pedro, Delgado-Ferreiro, Ignacio, Cappel, Ute B., Castro-García, Socorro, Sánchez-Andújar, Manuel, Bermúdez-García, Juan Manuel, Señarís-Rodríguez, María Antonia
• Format: Article
• Language: English
• Subjects: A-cation volume; Dicyanamide compounds; Hybrid organic-inorganic perovskites; Promolecule isosurface; Tolerance factor
• ISSN: 0022-4596; 1095-726X; 1095-726X
• DOI: 10.1016/j.jssc.2022.123635

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. [Display omitted] •Tolerance factors that stabilize the perovskite structure in [A][Mn(dca)3] hybrids.•A simple approach to calculate the size of large and anisotropic A-cations in HOIPs.•Useful methodology to design new hybrid perovskites with large A-cations.