Guha Shramana, Bera Suman, Garai Arghyadeep, Sarma D D, Pradhan Narayan, Acharya Somobrata
School of Applied & Interdisciplinary Sciences, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, India.
School of Materials Sciences, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, India.
J Am Chem Soc. 2024 Dec 11;146(49):33883-33892. doi: 10.1021/jacs.4c12490. Epub 2024 Nov 26.
Chirality is a ubiquitous feature in biological systems and occurs even in certain inorganic crystals. Interestingly, some inorganic nanocrystals have been shown to possess chirality, despite their achiral bulk forms. However, the mechanism of chirality formation and chiroptical responses in such nanocrystals is still ambiguous due to the presence of chiral organic ligands used to passivate such nanocrystals. Here, we recognize chiroptical responses from lead halide perovskite nanowires with different length scales. Cube-connected nanowires with minimum interfacial contacts make their arrangement chiral for chiroptical responses even in the absence of chiral ligands. The chiral nanowires with varying lengths serve as a systematic platform for improving dissymmetric factors significantly with increasing lengths. The dissymmetric factor of the longest nanowires reaches 1.4 × 10, which is the highest among the intrinsic chiral perovskite nanocrystals at present. The nanowires generate circularly polarized luminescence, which has been seldom reported in halide perovskite nanocrystals in the absence of any chiral ligands. Furthermore, we find that chirality exists in the basic unit consisting of two corner-connected cubes in the form of a dimer. The intrinsic chirality of the nanowires is determined by the lattice rotation of connected cubes along the interfacial boundaries, which is different from the commonly observed chirality induced by chiral ligands. Such chiral lead halide perovskite nanocrystals with robust chiroptical properties provide an ideal platform for understanding the origin of intrinsic chirality and the rational design of anisotropic chiral nanostructures.
手性是生物系统中普遍存在的特征,甚至在某些无机晶体中也会出现。有趣的是,一些无机纳米晶体尽管其块状形式是非手性的,但已被证明具有手性。然而,由于用于钝化此类纳米晶体的手性有机配体的存在,此类纳米晶体中手性形成和手性光学响应的机制仍不明确。在这里,我们识别了不同长度尺度的卤化铅钙钛矿纳米线的手性光学响应。具有最小界面接触的立方连接纳米线,即使在没有手性配体的情况下,其排列也具有手性以产生手性光学响应。长度不同的手性纳米线作为一个系统平台,随着长度增加可显著提高不对称因子。最长纳米线的不对称因子达到1.4×10,这是目前本征手性钙钛矿纳米晶体中最高的。这些纳米线产生圆偏振发光,在没有任何手性配体的卤化钙钛矿纳米晶体中很少有报道。此外,我们发现由两个角连接的立方体组成的二聚体形式的基本单元中存在手性。纳米线的本征手性由连接立方体沿界面边界的晶格旋转决定,这与通常观察到的由手性配体诱导的手性不同。这种具有强大手性光学性质的手性卤化铅钙钛矿纳米晶体为理解本征手性的起源和各向异性手性纳米结构的合理设计提供了一个理想平台。