Switchable Nonlinear Optical and Tunable Luminescent Properties Triggered by Multiple Phase Transitions in a Perovskite-Like Compound

Abstract

A new perovskite-like inorganic-organic hybrid compound [Et(n-Pr)P][Cd(dca)] (1) (where [Et(n-Pr)P] is the propyltriethylphosphonium cation and dca is a dicyanamide ligand) was discovered to undergo three reversible phase transitions at 270 K (T), 386 K (T), and 415 K (T), respectively. The variable-temperature single-crystal X-ray structural analyses reveal that these sequential phase transitions originate from the deformations of the [Cd(dca)] frameworks and the concomitant reorientations of the [Et(n-Pr)P] guest cations. It is found that 1 possesses a sensitive nonlinear optical (NLO) switching at T with a large contrast of ∼40 within a narrow temperature range of ∼7 K. Furthermore, 1 shows intriguing photoluminescence (PL) property, and the PL intensity suffers a plunge near T. The multiple phase transitions, switchable NLO and tunable luminescent properties simultaneously exist in this inorganic-organic perovskite-like hybrid compound, suggesting its great potential application in molecular switches and photoelectric field.

Tilts and shifts in molecular perovskites

“…By way of example, the high-temperature Cmce phase of [Et 3 PIJCH 2 ) 2 F]CdijNIJCN) 2 ] 3 is isostructural to [(CH 3 ) 2 NH 2 ]MnIJN 3 ) 3 at ambient conditions, but distinct from the Cmce phase of [Et 3 PPr]CdijNIJCN) 2 ] 3 (Et = ethyl, Pr = propyl). 13,37,55 Likewise, the Ibam symmetries of [Et 3 PPr]CdijNIJCN) 2 ] 3 and [NPr 4 ]FeijNIJCN) 2 ] 3 arise from different distortion modes and these systems are therefore not isostructural. 55,56 However, the Ibam and Cmce phases of [Et 3 PPr]CdijNIJCN) 2 ] 3 presented in ref.…”

“…13,37,55 Likewise, the Ibam symmetries of [Et 3 PPr]CdijNIJCN) 2 ] 3 and [NPr 4 ]FeijNIJCN) 2 ] 3 arise from different distortion modes and these systems are therefore not isostructural. 55,56 However, the Ibam and Cmce phases of [Et 3 PPr]CdijNIJCN) 2 ] 3 presented in ref. 55 were only roughly refined due to suboptimal data quality.…”

Structure and applications of organotin complex based on trimethyltin cation and quinaldic acid

“…The emission band centred at 368 nm corresponds to the lowest π–π* state in the ligand. On the other hand, the emission band at 430 nm may be attributed to metal‐to‐ligand charge transfer …”

Optical‐Dielectric Duple Bistable Switches: Photoluminescence of Reversible Phase Transition Molecular Material

“…Scanning temperature change rate is about 10 KMin À1 .A ll dielectric data were acquired on the TH2828A impedance analyzer with an applied electric field of 0.5 V. PL emission spectra and UVvis absorption spectra measurements were described previously. [13] CCDC 1920932-1920933 contains the supplementary crystallographic structure at 223 Ka nd 333 Kf or this paper.T hese data are provided free of charge by The Cambridge Crystallographic Data Centre. CCDC 1920932 (223 K) and 1920933(333 K).…”