Crystal Design for Tuning the Mechanical Flexibilities of M(salophen) Complexes
Crystal Design for Tuning the Mechanical Flexibilities of M(salophen) Complexes
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DOI：
10.1021/acs.cgd.2c01398
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发表时间：
2023-02
期刊：
影响因子：
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通讯作者：
Y. Sekine;Sotaro Kusumoto;Akira Sugimoto;Manabu Nakaya;S. Hayami
中科院分区：
文献类型：
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作者：
Y. Sekine;Sotaro Kusumoto;Akira Sugimoto;Manabu Nakaya;S. Hayami
弹性晶体是一类新型的光电子和太阳能电池材料。尽管在开发功能性软晶体时控制机械柔性是至关重要的，但所报道的基于金属配位络合物的弹性晶体的数量有限。当开发这样的晶体时，晶体的柔性可以通过中心金属的配体取代或通过中心金属离子的交换来调节;然而，迄今为止这还没有通过实验证明。因此，我们在此报告的机械灵活的化合物的制备使用的合成过程的基础上的金属配位络合物。结果发现，填充结构是相当大的结晶溶剂的影响，和控制的包装过程是至关重要的，在获得复杂的分子与设计的灵活性和结构。此外，我们证明了新的Pd和Pt配合物与salophen配体，表现出第二和第三高的弹性应变（ε值），分别报告日期，和最高和第二高的ε值（ε = 11.95%的Pd; 10.65%的Pt），分别在金属配合物。这些效应可以归因于金属和配体之间的键距的微观变化。我们的研究结果有望激发基于金属络合物的柔性晶体的调整和发展。
Elastic crystals are a novel class of materials for use in optoelectronics and solar cells. Although controlling mechanical flexibility is critical when developing functional soft crystals, the number of reported metal-coordination-complex-based elastic crystals is limited. When developing such crystals, the flexibility of the crystals may be tuned via ligand substitution of the central metals or by exchange of the central metal ions; however, this has not been demonstrated experimentally to date. Thus, we herein report the preparation of mechanically flexible compounds using a synthetic procedure based on metal coordination complexes. It was found that the packing structure was considerably affected by the crystallization solvent, and control over the packing process was critical in obtaining complex molecules with designed flexibilities and structures. Furthermore, we demonstrate new Pd and Pt complexes with the salophen ligand, which exhibit the second and third highest elastic strains (ε values) reported to date, respectively, and the highest and second highest ε values (ε = 11.95% for Pd; 10.65% for Pt), respectively, among metal coordination complexes. These effects can be attributed to the microscopic changes in bond distance between the metals and ligands. Our findings are expected to inspire the tuning and development of metal-complex-based flexible crystals.