Discovery of molecular ferroelectric catalytic annulation for quinolines.

Ferroelectrics as emerging and attractive catalysts have shown tremendous potential for applications including wastewater treatment, hydrogen production, nitrogen fixation, and organic synthesis, etc. In this study, we demonstrate that molecular ferroelectric crystal TMCM-CdCl3 (TMCM = trimethylchloromethylammonium) with multiaxial ferroelectricity and superior piezoelectricity has an effective catalytic activity on the direct construction of the pharmacologically important substituted quinoline derivatives via one-pot [3 + 2 + 1] annulation of anilines and terminal alkynes by using N,N-dimethylformamide (DMF) as the carbon source. The recrystallized TMCM-CdCl3 crystals from DMF remain well ferroelectricity and piezoelectricity. Upon ultrasonic condition, periodic changes in polarization contribute to the release of free charges from the surface of the ferroelectric domains in nano size, which then quickly interacts with the substrates in the solution to trigger the pivotal redox process. Our work advances the molecular ferroelectric crystal as a catalytic route to organic synthesis, not only providing valuable direction for molecular ferroelectrics but also further enriching the executable range of ferroelectric catalysis.

A Multiferroic Spin-Crossover Molecular Crystal.

Spin-crossover (SCO) ferroelectrics with dual-function switches have attracted great attention for significant magnetoelectric application prospects. However, the multiferroic crystals with SCO features have rarely been reported. Herein, a molecular multiferroic Fe(II) crystalline complex [FeII(C8-F-pbh)2] (1-F, C8-F-pbh = (1Z,N'E)-3-F-4-(octyloxy)-N'-(pyridin-2-ylmethylene)-benzo-hydrazonate) showing the coexistence of ferroelectricity, ferroelasticity, and SCO behavior is presented for the first time. By H/F substitution, the low phase transition temperature (270 K) of the non-fluorinated parent compound is significantly increased to 318 K in 1-F, which exhibits a spatial symmetry breaking 222F2 type ferroelectric phase transition with clear room-temperature ferroelectricity. Besides, 1-F also displays a spin transition between high- and low-spin states, accompanied by the d-orbital breaking within the t2g 4eg 2 and t2g 6eg° configuration change of octahedrally coordinated FeII center. Moreover, the 222F2 type ferroelectric phase transition is also a ferroelastic one, verified by the ferroelectric domains reversal and the evolution of ferroelastic domains. To the knowledge, 1-F is the first multiferroic SCO molecular crystal. This unprecedented finding sheds light on the exploration of molecular multistability materials for future smart devices.

A chiral two-dimensional perovskite-like lead-free bismuth(III) iodide hybrid with high phase transition temperature.

Bismuth(III) iodide perovskites have attracted great attention as lead-free hybrid semiconductors, but they mainly show zero- and one-dimensional structures. Herein, we report the first two-dimensional chiral perovskite-like bismuth(III) iodide hybrid [(S)-3-aminopyrrolidinium I]2Bi2/3I4 (1) with a high phase transition temperature of 408.8 K, higher than most of the reported chiral lead-free hybrid semiconductors.

A photoluminescent chiral lead-free hybrid ferroelastic semiconductor with switchable second-harmonic generation.

Chiral organic-inorganic hybrid semiconductors (COIHSs) dominated by lead halides have recently gained tremendous interest. Here, we report a lead-free photoluminescent COIHS [R-3-hydroxylpiperidinium]2SbCl5 with a bandgap of 3.14 eV. It shows a ferroelastic phase transition at 341 K accompanied by a switchable second-harmonic generation response and presents clear ferroelastic domains, which are rarely found in lead-free COIHSs.

An unprecedented azobenzene-based organic single-component ferroelectric.

Organic single-component ferroelectrics, as an important class of metal-free ferroelectrics, are highly desirable because of their easy processing, mechanical flexibility, and biocompatibility. However, although nearly 50 years have passed since the discovery of photochromism in azobenzene-doped cholesteric liquid crystals, ferroelectricity has never been found in azobenzene-based crystals. Here, we use an amino group to substitute a fluorine atom of 2,2',4,4',6,6'-hexafluoroazobenzene, which successfully introduces ferroelectricity into 2-amino-2',4,4',6,6'-pentafluoroazobenzene (APFA). APFA shows an extremely high Curie temperature (T c) of 443 K, which is outstanding among single-component ferroelectrics. It also exhibits an indirect optical band gap of 2.27 eV as well as photoisomerization behavior between the trans-form and the cis-form triggered by pedal motion. To our knowledge, APFA is the first azobenzene-based ferroelectric crystal. This work opens an avenue to design excellent single-component ferroelectrics and will inspire the exploration of azobenzene-based ferroelectrics for promising applications in biofriendly ferroelectric devices.