Jahn-Teller Effect on Framework Flexibility of Hybrid Organic-inorganic Perovskites

Here we study the Jahn–Teller (JT) effect on framework flexibility of two analogous hybrid organic–inorganic perovskites, [C(NH2)3][Zn(HCOO)3] (1-Zn) and [C(NH2)3][Cu(HCOO)3] (2-Cu). Single-crystal nanoindentation measurements show that the elastic moduli and hardnesses of 1-Zn are up to ∼52.0% and ∼25.0% greater than those of the JT active 2-Cu. Temperature-dependent X-ray diffraction measurements indicate that the thermal expansion along the b-axis is switched from negative to positive by replacing Zn2+ with Cu2+ on the B-site. These stark distinctions in framework flexibility are primarily attributed to the ∼10.0% elongation of Cu–O bonds induced by the JT effect and associated alterations in octahedral tilting and hydrogen-bonding. Our results demonstrate the prominence of the JT effect in the emerging hybrid perovskites and highlight the possibilities of tuning materials’ properties using orbital order.