Hafnium-Based Chiral 2D Organic–Inorganic Hybrid Metal Halides: Engineering Polarity and Nonlinear Optical Properties via Para-Substituent Effects

Two-dimensional (2D) organic–inorganic hybrid metal halides (OIMHs), characterized by noncentrosymmetric structures arising from the incorporation of chiral organic molecules that break inversion symmetry, have attracted significant attention. Particularly, chiral-polar 2D OIMHs offer a unique platform for multifunctional applications, as the coexistence of chirality and polarity enables the simultaneous manifestation of distinct properties such as nonlinear optical (NLO) effects, circular dichroism (CD), and ferroelectricity. In this study, we report the first synthesis of hafnium (Hf)-based chiral 2D OIMHs, achieved through the strategic incorporation of para-substituents on the benzene ring of chiral organic components. By tuning the substituents, we successfully modulate the polarity of the crystal structures, resulting in both chiral-nonpolar and chiral-polar systems. Our analysis of structural and optical properties, supported by density functional theory calculations, demonstrates that the polarity of these materials can be systematically tuned, enabling adjustable band gaps and CD in the UV range (200–280 nm). Notably, halogen substitution at the para-position of the benzene ring in the organic layer produces tunable optical band gaps ranging from 4.33 to 4.48 eV, the widest reported to date for chiral-polar 2D OIMHs. Furthermore, these materials exhibit enhanced NLO properties, including a remarkable 3.3-fold increase in second-harmonic generation intensity in chiral-polar compounds compared to their chiral-nonpolar counterparts. These findings position Hf-based chiral 2D OIMHs as promising candidates for UV-region applications, such as UV NLO devices and self-driven circularly polarized light detectors, offering new opportunities for designing multifunctional optoelectronic materials by harnessing the interplay between chirality and polarity.