Duary Subrata, Jana Arijit, Das Amitabha, Acharya Swetashree, Kini Amoghavarsha Ramachandra, Roy Jayoti, Poonia Ajay Kumar, Patel Deepak Kumar, Yadav Vivek, Antharjanam P K Sudhadevi, Pathak Biswarup, Kumaran Nair Valsala Devi Adarsh, Pradeep Thalappil
DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of Technology, Madras, Chennai 600036, India.
Department of Chemistry, Indian Institute of Technology Indore, Indore 453552, India.
Inorg Chem. 2024 Oct 7;63(40):18727-18737. doi: 10.1021/acs.inorgchem.4c02617. Epub 2024 Sep 25.
Atomically precise copper nanoclusters (NCs) attract research interest due to their intense photoluminescence, which enables their applications in photonics, optoelectronics, and sensing. Exploring these properties requires carefully designed clusters with atomic precision and a detailed understanding of their atom-specific luminescence properties. Here, we report two copper NCs, [Cu(MNA)(DPPE)] and [Cu(MNA-H)], shortly Cu and Cu, protected by 2-mercaptonicotinic acid (MNA-H) and 1,2-bis(diphenylphosphino)ethane (DPPE), showing "turn-off" mechanoresponsive luminescence. Single-crystal X-ray diffraction reveals that in the Cu cluster, two Cu units are appended with two thiols, forming a flattened boat-shaped CuS kernel, while in the Cu cluster, two Cu units form an adamantane-like CuS kernel. High-resolution electrospray ionization mass spectrometry studies reveal the molecular nature of these clusters. Lifetime decay profiles of the two clusters show the average lifetimes of 0.84 and 1.64 μs, respectively. These thermally stable Cu NCs become nonluminescent upon mechanical milling but regain their emission upon exposure to solvent vapors. Spectroscopic data of the clusters match well with their computed electronic structures. This work expands the collection of thermally stable and mechanoresponsive luminescent coinage metal NCs, enriching the diversity and applications of such materials.
原子精确的铜纳米团簇（NCs）因其强烈的光致发光而吸引了研究兴趣，这使其能够应用于光子学、光电子学和传感领域。探索这些性质需要精心设计具有原子精度的团簇，并详细了解其原子特异性发光性质。在此，我们报道了两种由2-巯基烟酸（MNA-H）和1,2-双（二苯基膦基）乙烷（DPPE）保护的铜纳米团簇，[Cu(MNA)(DPPE)]和[Cu(MNA-H)]，简称Cu和Cu，它们表现出“关断”机械响应发光。单晶X射线衍射表明，在Cu团簇中，两个Cu单元与两个硫醇相连，形成一个扁平的船形CuS核，而在Cu团簇中，两个Cu单元形成一个类金刚烷的CuS核。高分辨率电喷雾电离质谱研究揭示了这些团簇的分子性质。这两个团簇的寿命衰减曲线分别显示平均寿命为0.84和1.64 μs。这些热稳定的铜纳米团簇在机械研磨时变得不发光，但在暴露于溶剂蒸汽时恢复发光。团簇的光谱数据与其计算的电子结构匹配良好。这项工作扩展了热稳定和机械响应发光的铸币金属纳米团簇的种类，丰富了此类材料的多样性和应用。
