Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 9, Issue 4, Pages 751-755Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.7b03229
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Funding
- National Natural Science Foundation of China [21571072, 11374114, 10974062]
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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 similar to 52.0% and similar to 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 similar to 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.
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