Spatially Correlated Chirality in Chiral Two-Dimensional Perovskites Revealed by Second-Harmonic-Generation Circular Dichroism Microscopy.

Understanding the chiral mechanism of chiral hybrid perovskites is a prerequisite for developing relevant chiroptoelectronic applications. Although conventional circular dichroism (CD) spectroscopy can be used to characterize chirality in chiral perovskites, it has a low signal-to-noise ratio and can provide only information about macroscopic chirality. Herein, with the aim of revealing the microscopic chiral mechanism in chiral perovskites, we utilize a spacer cation alloying strategy to construct chiral two-dimensional perovskites. For the first time, we demonstrate second-harmonic-generation CD microarea imaging in chiral perovskite thin films to unveil their spatially correlated chirality. In combination with theoretical calculations, it is revealed that the spatially correlated chirality is caused by localized out-of-plane supramolecular orientations. This work will not only advance the understanding of the mechanism of chiroptical activity in chiral perovskites but also provide inspiration for the rational design and synthesis of perovskites for chirality-related nonlinear optoelectronic devices.

Chirality-Dependent Second-Order Nonlinear Optical Effect in 1D Organic-Inorganic Hybrid Perovskite Bulk Single Crystal.

The introduction of chirality into organic-inorganic hybrid perovskites (OIHPs) is expected to achieve excellent photoelectric and nonlinear materials related to circular dichroism. Owing to the existence of asymmetric center and intrinsic chirality in the chiral OIHPs, the different efficiencies of second harmonic generation (SHG) signal occurs when the circularly polarized light (CPL) with different phases passes through the chiral crystal, which is defined as second harmonic generation circular dichroism (SHG-CD). Here, the SHG-CD effect is developed in bulk single crystals of chiral one-dimensional (1D) [(R/S)-3-aminopiperidine]PbI4 . It is the first time that CPL is distinguished using chirality-dependent SHG-CD effect in OIHPs bulk single crystals. Such SHG-CD technology extends the detection range to near infrared region (NIR). In this way, the anisotropy factor (gSHG-CD ) through SHG-CD signal is as high as 0.21.

Spectroscopy for model heterogeneous asymmetric catalysis.

Heterogeneous catalysis has vastly benefited from investigations performed on model systems under well-controlled conditions. The application of most of the techniques utilized for such studies is not feasible for asymmetric reactions as enantiomers possess identical physical and chemical properties unless while interacting with polarized light and other chiral entities. A thorough investigation of a heterogeneous asymmetric catalytic process should include probing the catalyst prior to, during, and after the reaction as well as the analysis of reaction products to evaluate the achieved enantiomeric excess. I present recent studies that demonstrate the strength of chiroptical spectroscopic methods to tackle the challenges in investigating model heterogeneous asymmetric catalysis covering all the abovementioned aspects.