3D Organic–Inorganic Perovskite Ferroelastic Materials with Two Ferroelastic Phases: [Et₃P(CH₂)₂F][Mn(dca)₃] and [Et₃P(CH₂)₂Cl][Mn(dca)₃]

Abstract

Organic–inorganic hybrid perovskite‐type multiferroics have attracted considerable research interest owing to their fundamental scientific significance and promising technological applications in sensors and multiple‐state memories. The recent achievements with divalent metal dicyanamide compounds revealed such malleable frameworks as a unique platform for developing novel functional materials. Herein, two 3D organic–inorganic hybrid perovskites [Et3P(CH2)2F][Mn(dca)3] (1) and [Et3P(CH2)2Cl][Mn(dca)3] (2) (dca=dicyanamide, N(CN)2−) are presented. Accompanying the sequential phase transitions, they display a broad range of intriguing physical properties, including above room temperature ferroelastic behavior, switchable dielectricity, and low‐temperature antiferromagnetic ordering (Tc=2.4 K for both 1 and 2). It is also worth noting that the spontaneous strain value of 1 is far beyond that of 2 in the first ferroelastic phase, as a result of the precise halogen substitution. From the point view of molecular design, this work should inspire further exploration of multifunctional molecular materials with desirable properties.

Room-temperature ferroelectric and ferroelastic orders coexisting in a new tetrafluoroborate-based perovskite

“…[4][5][6][7][8][9][10] In particular, the ABX 3 -type molecular perovskites, in which each site can be hold by diverse components, are regarded as an important host-guest structural model for searching molecule-based multiferroic materials. [11][12][13][14][15][16][17] For example, some metal formate perovskites, (Me 2 NH 2 )[M(HCOO) 3 ] (M = Mn II , Fe II , Co II , Ni II ), 18 reveal magnetic and electric orders at below 36 K. Two ferroelastic perovskites, (Et 3 P(CH 2 ) 2 F/Et 3 P(CH 2 ) 2 Cl)-[Mn(N(CN) 2 ) 3 ], 19 display antiferromagnetic orders at below 2.4 K. An azido perovskites, (Me 4 N)[Mn(N 3 ) 3 ], 20,21 was suggested as a multiferroic material coexisting antiferroelectricity, ferroelasticity, and magnetic bistabilities at room temperature. Nevertheless, the multiferroic materials with coexistence of ferroelectric and ferroelastic orders, especially those occur at above room temperature, are very scarce.…”

Precise design and preparation of two 3D organic–inorganic perovskite ferroelectrics (1,5-diazabicyclo[3.2.2]nonane)RbX3 (X = Br, I)

“…The commonly reported organic amines are only limited to methylamine and formamidine with small size, 28 while most of the metals are lead, tin, and antimony. [29][30][31][32][33][34][35] In 2010, a 3D alkali halide perovskite [2. (2).…”

Two metal-free perovskite molecules with different 3D frameworks show reversible phase transition, dielectric anomaly and SHG effect

“…At present, the discovered HOIP halide crystals with face- and corner-sharing modes are found in compounds. 63–65 However, the organic–inorganic ammonium halide crystal structure containing only planes and corners has not yet been found.…”