Soft porous coordination polymers are a new class of materials that have the potential to combine favorable features of metal–organic polyhedra (MOP) and frameworks (MOFs) with those of soft materials: permanent porosity and chemical specificity with processability and optical, electronic, and mechanical responses. Fundamental studies are needed to guide the future technological applications of these materials. We employ topologically-based algorithms to generate crystalline structures in the fcu topology and use classical molecular modeling to calculate their mechanical properties. The generated crystals used dimetal paddlewheel based MOP with cuboctahedral topology [M₂(bdc)₂]₁₂ (M = Co, Cu, Rh, and Zn; bdc = 1,3-benzenedicarboxylate) as the nodes and 1,4-diazabicyclo[2.2.2]octane (DABCO), bipyridine, 1,4-bis(imidazol-1-ylmethyl)benzene (bix), 4,4′-bis(imidazol-1-ylmethyl)biphenyl (bibPh), and 1,1′-(1,12-dodecanediyl)bis[1H-imidazole] (bidod) as the linkers. Structures containing DABCO or bipyridine are found to have bulk moduli approximately an order of magnitude higher than those containing bix, bibPh, or bidod. The differences in mechanical properties are associated with the linker flexibility, as evidenced by free energy calculations on the radius of gyration of the linkers. We also calculate free energies as a function of radius of gyration of chosen nanoparticles.

中文翻译：

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了解接头柔性在软质多孔配位聚合物中的作用

软质多孔配位聚合物是一类新型材料，具有将金属有机多面体（MOP）和骨架（MOF）的有利特征与软质材料相结合的潜力：永久孔隙度和化学特殊性以及可加工性，光学，电子和化学性能。机械响应。需要进行基础研究来指导这些材料的未来技术应用。我们采用基于拓扑的算法在fcu拓扑中生成晶体结构，并使用经典的分子模型来计算其机械性能。生成的晶体使用具有双八面体拓扑[M ₂（bdc）₂ ] _12的基于双金属桨轮的MOP（M = Co，Cu，Rh和Zn； bdc = 1,3-苯二甲酸）作为结点和1,4-二氮杂双环[2.2.2]辛烷（DABCO），联吡啶，1,4-双（咪唑-1） -（甲基）苯（bix），4,4'-双（咪唑-1-基甲基）联苯（bibPh）和1,1'-（1,12-十二烷二基）双[1 H-咪唑]（bidod）为链接器。发现含有DABCO或联吡啶的结构的体积模量比含有bix，bibPh或二氧化钛的结构的模量高约一个数量级。机械性能的差异与接头的柔韧性有关，这由接头的回转半径的自由能计算证明。我们还计算自由能与所选纳米粒子的回转半径的函数关系。