Diverse Rotational Flexibility of Substituted Dicarboxylate Ligands in Functional Porous Coordination Polymers
Diverse Rotational Flexibility of Substituted Dicarboxylate Ligands in Functional Porous Coordination Polymers
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DOI：
10.1021/acs.jpcc.5b10393
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发表时间：
2015-12-31
影响因子：
3.7
通讯作者：
Nagaoka, Masataka
中科院分区：
文献类型：
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作者：
Pakhira, Srimanta;Takayanagi, Masayoshi;Nagaoka, Masataka
在由不同二元酸配体组成的多孔配位聚合物(PCPs)的孔道中进行自由基聚合是控制产物规整性的一种很有前途的方法。然而，不同的配体如何有助于控制战术性仍然是个谜。在这里，我们预测了二羧酸配体的转动在控制中的重要作用，并结合一个模型系统研究了一系列PCP的转动基团的几何结构、稳定性、势能曲线和转动能垒。采用关联一致性双C质量基组的色散修正密度泛函理论方法和修正密度泛函理论方法。我们揭示了配体相关的平衡平面和非平面结构以及从刚性57.74到柔性10.45kJ·mol(-1)的大范围的转动势垒。通过将二羧酸盐配体的力场参数与所获得的旋转行为进行拟合，未来使用柔性PCP模型进行分子动力学模拟研究将为控制分子规整性的机制提供分子见解。
The radical polymerization in the channels of porous coordination polymers (PCPs) composed of different dicarboxylate ligands has been reported as a promising approach to control the tacticity of product polymers. However, it is still elusive how the different ligands contribute to control the tacticity. Here we anticipate an important role of the rotation of the dicarboxylate ligands in the control and have investigated the geometrical structure, stability, potential energy curves, and rotational energy barriers of the rotational groups of a series of PCPs considering a model system. Both the dispersion-uncorrected and corrected density functional theory methods with the correlation consistent double-C quality basis set have been applied. We have revealed the ligand-dependent equilibrium planar and nonplanar structures and a wide range of rotational barriers, from rigid 57.74 to flexible 10.45 kJ mol(-1). By fitting the force field parameters of the dicarboxylate ligands to the obtained rotational behaviors, future molecular dynamics simulation studies with the flexible PCP models will provide molecular insights into the mechanism of the control of tacticity.