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Manifestation of Structural Differences of Atomically Precise Cluster-Assembled Solids in Their Mechanical Properties
Chemistry of Materials ( IF 7.2 ) Pub Date : 2020-08-21 , DOI: 10.1021/acs.chemmater.0c02905 Korath Shivan Sugi 1 , Payel Bandyopadhyay 2 , Mohammad Bodiuzzaman 1 , Abhijit Nag 1 , Manjapoyil Hridya 1 , Wakeel Ahmed Dar 1 , Pijush Ghosh 2 , Thalappil Pradeep 1
Chemistry of Materials ( IF 7.2 ) Pub Date : 2020-08-21 , DOI: 10.1021/acs.chemmater.0c02905 Korath Shivan Sugi 1 , Payel Bandyopadhyay 2 , Mohammad Bodiuzzaman 1 , Abhijit Nag 1 , Manjapoyil Hridya 1 , Wakeel Ahmed Dar 1 , Pijush Ghosh 2 , Thalappil Pradeep 1
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Cluster-assembled solids (CASs) formed by the self-assembly of monodispersed atomically precise monolayer-protected noble metal clusters are attractive due to their collective properties. The physical stability and mechanical response of these materials remain largely unexplored. We have investigated the mechanical response of single crystals of atomically precise dithiol-protected Ag29 polymorphs, monothiol-protected Ag46, and a cocrystal of the latter with Ag40 (formulas of the clusters have been simplified merely with the number of metal atoms). The Ag29 polymorphs crystallize in cubic and trigonal lattices (Ag29 C and Ag29 T, respectively), and Ag46 and its cocrystal with Ag40 crystallize in trigonal and monoclinic lattices (Ag46 T and Ag40/46 M, respectively). The time and loading-rate-dependent mechanical properties of the CASs are elucidated by measuring nanoindentation creep and stress relaxation. The obtained Young’s modulus (Er) values of the CASs were similar to those of zeolitic imidazolate frameworks (ZIFs) and show the trend Ag29 T > Ag29 C > Ag40/46 M > Ag46 T. We have also studied the viscoelastic properties of all of the four CASs and found that the value of tan δ/damping factor of monothiol-protected Ag46 T was higher than that of other CASs. The unusual mechanical response of CASs was attributed to the supramolecular interactions at the surface of nanoclusters. This observation implies that the stiffness and damping characteristics of the materials can be modulated by ligand and surface engineering. These studies suggest the possibility of distinguishing between the crystal structures using mechanical properties. This work provides an understanding that is critical for designing nanocluster devices capable of withstanding mechanical deformations.
中文翻译：
原子精确簇组装固体的机械性能表现出结构差异
通过单分散原子精确的单层保护的贵金属簇的自组装而形成的簇组装固体（CAS）具有吸引人的特性。这些材料的物理稳定性和机械响应在很大程度上尚待探索。我们研究了原子精确的二硫醇保护的Ag 29多晶型物，单硫醇保护的Ag 46以及后者与Ag 40的共晶体的单晶的机械响应（仅通过金属原子数简化了团簇的组成） 。Ag 29多晶型物以立方和三角形晶格结晶（分别为Ag 29 C和Ag 29 T），以及Ag 46其与Ag 40的共晶结晶为三角形和单斜晶格（分别为Ag 46 T和Ag 40/46 M）。通过测量纳米压痕蠕变和应力松弛来阐明CAS的时间和加载速率相关的机械性能。将所获得的杨氏模量（Ë - [R ）卡斯的值的那些相似沸石咪唑骨架（ZIF）的并显示趋势的Ag 29 T>的Ag 29 C>银46分之40 M>的Ag 46 T.我们还研究了四个CAS的粘弹性，发现单硫醇保护的Ag 46的tanδ/阻尼因子值T高于其他CAS。CASs的异常机械响应归因于纳米团簇表面的超分子相互作用。该观察结果暗示可以通过配体和表面工程来调节材料的刚度和阻尼特性。这些研究表明利用机械性能区分晶体结构的可能性。这项工作提供了对于设计能够承受机械变形的纳米簇设备至关重要的理解。
更新日期：2020-09-22
中文翻译：
原子精确簇组装固体的机械性能表现出结构差异
通过单分散原子精确的单层保护的贵金属簇的自组装而形成的簇组装固体（CAS）具有吸引人的特性。这些材料的物理稳定性和机械响应在很大程度上尚待探索。我们研究了原子精确的二硫醇保护的Ag 29多晶型物，单硫醇保护的Ag 46以及后者与Ag 40的共晶体的单晶的机械响应（仅通过金属原子数简化了团簇的组成） 。Ag 29多晶型物以立方和三角形晶格结晶（分别为Ag 29 C和Ag 29 T），以及Ag 46其与Ag 40的共晶结晶为三角形和单斜晶格（分别为Ag 46 T和Ag 40/46 M）。通过测量纳米压痕蠕变和应力松弛来阐明CAS的时间和加载速率相关的机械性能。将所获得的杨氏模量（Ë - [R ）卡斯的值的那些相似沸石咪唑骨架（ZIF）的并显示趋势的Ag 29 T>的Ag 29 C>银46分之40 M>的Ag 46 T.我们还研究了四个CAS的粘弹性，发现单硫醇保护的Ag 46的tanδ/阻尼因子值T高于其他CAS。CASs的异常机械响应归因于纳米团簇表面的超分子相互作用。该观察结果暗示可以通过配体和表面工程来调节材料的刚度和阻尼特性。这些研究表明利用机械性能区分晶体结构的可能性。这项工作提供了对于设计能够承受机械变形的纳米簇设备至关重要的理解。
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