Liu Qiming, Song Xingjian, DuBois Davida, Yu Bingzhe, Bhuller Amrinder, Flannery Gabriel, Hawley Marcus, Bridges Frank, Chen Shaowei
Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, California 95064, United States.
Department of Physics, University of California, 1156 High Street, Santa Cruz, California 95064, United States.
Inorg Chem. 2024 Jan 15;63(2):1046-1053. doi: 10.1021/acs.inorgchem.3c03386. Epub 2024 Jan 3.
Metal chalcogenide nanoparticles play a vital role in a wide range of applications and are typically stabilized by organic derivatives containing thiol, amine, or carboxyl moieties, where the nonconjugated particle-ligand interfaces limit the electronic interactions between the inorganic cores and organic ligands. Herein, a wet-chemistry method is developed for the facile preparation of stable platinum chalcogenide (S, Se) nanoparticles capped with acetylene derivatives (e.g., 4-ethylphenylacetylene, EPA). The formation of Pt-C≡ conjugated bonds at the nanoparticle interfaces, which is confirmed by optical and X-ray spectroscopic measurements, leads to markedly enhanced electronic interactions between the d electrons of the nanoparticle cores and π electrons of the acetylene moiety, in stark contrast to the mercapto-capped counterparts with only nonconjugated Pt-S- interfacial bonds, as manifested in spectroscopic measurements and density functional theory calculations. This study underscores the significance of conjugated anchoring linkages in the stabilization and functionalization of metal chalcogenides, a unique strategy for diverse applications.
金属硫族化物纳米颗粒在广泛的应用中起着至关重要的作用，通常由含有硫醇、胺或羧基部分的有机衍生物来稳定，其中非共轭的颗粒-配体界面限制了无机核与有机配体之间的电子相互作用。在此，开发了一种湿化学方法，用于简便地制备由乙炔衍生物（如4-乙基苯乙炔，EPA）包覆的稳定的铂硫族化物（S，Se）纳米颗粒。通过光学和X射线光谱测量证实，在纳米颗粒界面处形成了Pt-C≡共轭键，这导致纳米颗粒核的d电子与乙炔部分的π电子之间的电子相互作用显著增强，这与仅具有非共轭Pt-S-界面键的巯基包覆的对应物形成鲜明对比，这在光谱测量和密度泛函理论计算中得到了体现。这项研究强调了共轭锚定键在金属硫族化物的稳定化和功能化中的重要性，这是一种用于多种应用的独特策略。
