An Lian-Cai, Li Xiang, Li Zhi-Gang, Li Qite, Beldon Patrick J, Gao Fei-Fei, Li Zi-Ying, Zhu Shengli, Di Lu, Zhao Sanchuan, Zhu Jian, Comboni Davide, Kupenko Ilya, Li Wei, Ramamurty U, Bu Xian-He
School of Materials Science and Engineering, Nankai University, 300350, Tianjin, China.
Institut für Mineralogie, University of Münster, Corrensstr. 24, 48149, Münster, Germany.
Nat Commun. 2022 Nov 4;13(1):6645. doi: 10.1038/s41467-022-34351-0.
Coordination polymers (CPs) are a class of crystalline solids that are considered brittle, due to the dominance of directional coordination bonding, which limits their utility in flexible electronics and wearable devices. Hence, engineering plasticity into functional CPs is of great importance. Here, we report plastic bending of a semiconducting CP crystal, Cu-Trz (Trz = 1,2,3-triazolate), that originates from delamination facilitated by the discrete bonding interactions along different crystallographic directions in the lattice. The coexistence of strong coordination bonds and weak supramolecular interactions, together with the unique molecular packing, are the structural features that enable the mechanical flexibility and anisotropic response. The spatially resolved analysis of short-range molecular forces reveals that the strong coordination bonds, and the adaptive C-H···π and Cu···Cu interactions, synergistically lead to the delamination of the local structures and consequently the associated mechanical bending. The proposed delamination mechanism offers a versatile tool for designing the plasticity of CPs and other molecular crystals.
配位聚合物（CPs）是一类晶体固体，由于定向配位键占主导地位，被认为是脆性的，这限制了它们在柔性电子器件和可穿戴设备中的应用。因此，将可塑性引入功能性CPs非常重要。在此，我们报道了一种半导体CP晶体Cu-Trz（Trz = 1,2,3-三唑）的塑性弯曲，其源于晶格中沿不同晶体学方向的离散键合相互作用促进的分层。强配位键和弱超分子相互作用的共存，以及独特的分子堆积，是实现机械柔韧性和各向异性响应的结构特征。对短程分子力的空间分辨分析表明，强配位键以及适应性的C-H···π和Cu···Cu相互作用协同导致局部结构的分层，进而导致相关的机械弯曲。所提出的分层机制为设计CPs和其他分子晶体的可塑性提供了一种通用工具。
