Yoshino Haruka, Saigo Masaki, Ehara Takumi, Miyata Kiyoshi, Onda Ken, Pirillo Jenny, Hijikata Yuh, Takaishi Shinya, Kosaka Wataru, Otake Ken-Ichi, Kitagawa Susumu, Miyasaka Hitoshi
Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577, Japan.
Department of Chemistry, Faculty of Science, Kyushu University, Motooka 744, Nishi-ku, Fukuoka, 819-0395, Japan.
Angew Chem Int Ed Engl. 2025 Jan 27;64(5):e202413830. doi: 10.1002/anie.202413830. Epub 2024 Dec 17.
Although a widely used and important industrial chemical, carbon disulfide (CS) poses a number of hazards due to its volatility and toxicity. As such, the development of multifunctional materials for the selective capture and easy recognition of CS is one of the crucial issues. Herein, we demonstrate completely selective CS adsorption among trials involving HO, alcohols, volatile organic compounds (including thiol derivatives), N, H, O, CH, CO, NO, and CO. We also showcase its fine detection using remarkable luminescent response in a gold(I)-based metal-organic framework (MOF) of {Zn(pz)[Au(CN)]} (pz=pyrazine; 1) with a two-fold interpenetration network. Ex situ single crystal X-ray diffraction for 1 and CS-accommodated 1 suggested that the Au ⋅⋅⋅ Au atoms are not only luminescent centers but also act as interaction sites for CS modulating the Au ⋅⋅⋅ Au contacts. These experiments revealed the specificity of CS and how changes in the CS-induced structure. Based on the obtained structural transformation, 1 exhibited a sensitive detecting ability for CS with an ultrafast response time of less than 10 s. Moreover, ex situ time-resolved photoluminescence analyses developed in this work implied that CS varied the energetic relaxation at the excited states related to the luminescent efficiency of the resultant MOF system.
尽管二硫化碳（CS₂）是一种广泛使用且重要的工业化学品，但由于其挥发性和毒性，它存在许多危害。因此，开发用于选择性捕获和易于识别CS₂的多功能材料是关键问题之一。在此，我们展示了在涉及H₂O、醇类、挥发性有机化合物（包括硫醇衍生物）、N₂、H₂、O₂、CH₄、CO₂、NO₂和CO₂的试验中对CS₂的完全选择性吸附。我们还展示了在具有双折互穿网络的{Zn(pz)[Au(CN)]}（pz = 吡嗪；1）的金（I）基金属有机框架（MOF）中使用显著的发光响应进行的精细检测。对1和容纳CS₂的1进行的非原位单晶X射线衍射表明，Au∙∙∙Au原子不仅是发光中心，而且还作为CS₂的相互作用位点，调节Au∙∙∙Au接触。这些实验揭示了CS₂的特异性以及CS₂诱导的结构变化。基于获得的结构转变，1对CS₂表现出灵敏的检测能力，超快响应时间小于10秒。此外，这项工作中开展的非原位时间分辨光致发光分析表明，CS₂改变了与所得MOF系统发光效率相关的激发态能量弛豫。
