A symmetry breaking phase transition-triggered high-temperature solid-state quadratic nonlinear optical switch coupled with a switchable dielectric constant in an organic–inorganic hybrid compound

Abstract

An organic-inorganic hybrid compound, [NH3(CH2)5NH3]SbCl5, exhibits a switchable second harmonic generation (SHG) effect between SHG-OFF and SHG-ON states and tunable dielectric behaviors between high and low dielectric states, connected with the changes in the dynamics of 1,5-pentanediammonium cations during its centrosymmetric-to-noncentrosymmetric symmetry breaking phase transition at 365.4 K.

An Above‐Room‐Temperature Phase Transition with Dielectric‐Switching Properties in a Halogenobismuthate(III) – Tris(Cyclohexylmethylammonium) Pentabromobismuthate(III) Bromide

“…In contrast to the one‐dimensional structural family R 2 MX 5 (R = organic cation; M = Sb, Bi; and X = Cl, Br, I),, , the free cavities between the anionic chains of 1 are occupied by both the CMA cations and uncoordinated Br – anions (Figure ). All of the C and N atoms of the CMA cations are located in general positions.…”

“…The Br–Bi–Br angles cis to each other fall in the range 85.39(4) to 95.62(4)°, which suggests that the BiBr 6 octahedron is severely distorted in the RTP. The Bi–Br–Bi bridging angle of 147.33(4)°, should be expanded by heating , , …”

“…Therefore, the exploration and design of high‐temperature phase‐transition materials with attractive dielectric properties is imperative and meaningful. Among the organic–inorganic compounds, the halogenoantimonate(III) and halogenobismuthate(III) compounds with the general formula R a M b X 3 b+a (R = organic cation, M = Sb III or Bi III , and X = Cl, Br, or I) have recently been shown to be candidates for high‐temperature phase transitions . However, compounds with the R 3 [MX 5 ][X] chemical composition containing polyanionic chains have only been observed sporadically …”

A nonlinear optical switch induced by an external electric field: inorganic alkaline–earth alkalide

“…53 Furthermore, some NLO switch molecules have been synthesized in the presence of external stimulator triggering: e.g. an acido-triggered second-order NLO switch photochromic cyclometallated platinum(II) complex, 73 a temperature-induced symmetry-breaking phase transition NLO switch 74 and so forth. Experimental investigations further demonstrate the possibility of the synthesis of a stimulator introduced NLO switch.…”

Phase Transition and Dielectric Response Originating from Disorder‐Order Transition in the In‐Based Organic‐Inorganic Hybrid Material [NH3(CH2)5NH3][InCl5(H2O)] ⋅ H2O

“…The space group of these two compounds changes from Pnma at 393 K to P2 1 2 1 2 1 at 293 K. The phase transition is ascribed to the disorder-order transformation of the 1,5-pentanediammonium cations. [24,25] In addition, a new perovskite-type organic-inorganic hybrid phase transition material, [NH 3 (CH 2 ) 5 NH 3 ][MnCl 4 ], which undergoes a reversible phase transition at 298 K. The disorder-order process of alkylenediammonium cations govern the phase transition process. [26] These studies suggest that alkylenediammonium cations are liable to undergo a disorder-order transformation.…”