ABSTRACT
The striking chemical variability of hybrid organic-inorganic metal halides (HOMHs) endows them with fascinating optoelectronic properties. The inorganic skeletons of HOMHs are often flexible and their lattice deformations could serve as an effective factor for enabling the functionalities of HOMHs. Here, the linear and nonlinear optical properties of zero-dimensional (0D) tin(IV) halides have been tuned by structural distortion facilitated by the chiral amines. Enantiopure α-methylbenzyl ammoniums (XMBA, X = Cl, F) effectively transfer their chirality to the inorganic scaffolds when forming the tin(IV) halides, which enables polar arrangements in their crystals and leads to outstanding second-order nonlinear optical performances. In contrast, the racemic mixture of R- and S-FMBA results in the formation of HOMHs with room temperature phosphorescence. The lower lattice deformation in (rac-FMBA)2SnCl6 restrains the non-radiative decay from electron-phonon coupling and facilitates the photoluminescence. Meanwhile, the marked π-π interaction stabilizes the T1 state for phosphorescent emission. These distinct linear and nonlinear optical properties denote the important role that the lattice distortion plays in tuning the optical properties of low-dimensional HOMHs, and offer a promising perspective of 0D tin(IV) halides for applications in optoelectronic materials and devices.
ABSTRACT
Chiral metal halides have shown great potential for application in next generation nonlinear optical (NLO) devices owing to their intrinsic non-centrosymmetry. However, the structures and properties of chiral hybrid indium halides have been rarely reported, especially when it comes to second-harmonic generation (SHG) in NLO. In this work, we have synthesized a pair of new zero-dimensional (0D) chiral hybrid indium halides, (R-MPEA)6InCl9 and (S-MPEA)6InCl9, and studied their NLO properties. The as-prepared chiral hybrid indium halides crystallize in non-centrosymmetric P3221 and P3121 space groups, respectively. NLO studies show that 0D chiral hybrid indium halide crystals exhibit strong SHG responses with high polarization ratio and high laser damage threshold (LDT). This work enriches the family of chiral hybrid metal halide materials and offers a feasible strategy for the targeted design and synthesis of intrinsically non-centrosymmetric metal halide materials for NLO applications.
