Branzi Lorenzo, Fitzsimmons Lucy, Gun'ko Yurii K
Department School of Chemistry, CRANN and AMBER Research Centres, Institution Trinity College Dublin Address, 1 College Green, Dublin, 2, Ireland.
Angew Chem Int Ed Engl. 2024 Oct 7;63(41):e202409313. doi: 10.1002/anie.202409313. Epub 2024 Sep 5.
Chirality in inorganic nanostructures has recently stimulated the attention of many researchers, both to unravel fundamental questions on the origin of chirality in inorganic and hybrid materials, as well as to introduce novel promising properties that are originated by the symmetry breaking. MoS is one of the most investigated among the large family of layered transition metal dichalcogenides. In particular, the metastable metallic 1T-MoS phase is of large interest for potential applications. However, due to thermodynamic reasons, the synthesis of 1T-MoS phase is quite challenging. Herein, we present the first synthesis of chiral 1T-MoS phase which shows remarkably high chiroptical activity with a g-factor up to 0.01. Chiral 1T-MoS was produced using tartaric acid as a chiral ligand to induce symmetry breaking during the material's growth under hydrothermal conditions, leading to the formation of distorted hierarchical nanosheet assemblies exhibiting chiral morphology. Thorough optimization of the synthetic conditions was carried out to maximize chiroptical activity, which is strongly related to the nanostructures' morphology. Finally, the formation mechanism of the chiral 1T-MoS nanosheet assemblies was investigated, focusing on the role of molecular intermediates in the growth of the nanosheets and the transfer of chirality.
无机纳米结构中的手性最近引起了许多研究人员的关注,这既有助于揭示无机和混合材料中手性起源的基本问题,也有助于引入由对称性破缺产生的具有前景的新特性。在层状过渡金属二硫属化物大家族中,二硫化钼是研究最多的之一。特别是,亚稳态金属1T-MoS相因其潜在应用而备受关注。然而,由于热力学原因,1T-MoS相的合成颇具挑战性。在此,我们首次合成了手性1T-MoS相,其表现出高达0.01的g因子,具有显著的高圆二色活性。手性1T-MoS是在水热条件下,以酒石酸作为手性配体诱导材料生长过程中的对称性破缺而制备的,从而形成了具有手性形态的扭曲分级纳米片组装体。我们对合成条件进行了全面优化,以最大化圆二色活性,该活性与纳米结构的形态密切相关。最后,研究了手性1T-MoS纳米片组装体的形成机制,重点关注分子中间体在纳米片生长和手性转移中的作用。