<br>具有氢键网络的木质纤维素糠基生物基聚二乙炔的晶体结构：通过改变间隔基长度影响固态聚合的方向,Crystal Growth & Design

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具有氢键网络的木质纤维素糠基生物基聚二乙炔的晶体结构：通过改变间隔基长度影响固态聚合的方向
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2022-04-12 , DOI: 10.1021/acs.cgd.2c00307
Pierre Baillargeon ₁ , Raphaël Robidas ₂ , Olivier Toulgoat ₁ , Zacharie Michaud ₁ , Claude Y Legault ₂ , Tarik Rahem ₁

Affiliation

我们提出了两种木质纤维素生物基丁二炔 (DA) 的拓扑化学聚合，其区别仅在于二炔和氨基甲酸酯官能团之间的烷基间隔基长度为 1 个亚甲基 ( n = 1) 或 3 个亚甲基单元 ( n = 3)。它们的结晶分子组织具有适合在两个潜在方向（平行于或倾斜于氢键（HB）网络）聚合的显着特征。然而，最终聚二乙炔 (PDA) 的单晶结构表明，这两种衍生物的共轭主链的最终取向是不同的，这导致n = 1 时形成 HB 超分子聚合物网络（2D 纳米片）和独立的线性 PDA 链分子内HBs的n = 3。因此，间隔基长度修饰可以被认为是影响共轭聚合物链分子取向的新策略，这对于开发具有最佳机械和光电性能的下一代材料至关重要。对模型低聚二乙炔进行计算，以评估 HBs 在不同结晶超分子堆积基序中的协同效应以及与 PDA 链共轭主链扭转相关的能量分布（即，其采用平面或螺旋构象的能力）。

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Crystal Structures of Lignocellulosic Furfuryl Biobased Polydiacetylenes with Hydrogen-Bond Networks: Influencing the Direction of Solid-State Polymerization through Modification of the Spacer Length

We present the topochemical polymerization of two lignocellulosic biobased diacetylenes (DAs) that only differ by an alkyl spacer length of 1 methylene (n = 1) or 3 methylene units (n = 3) between the diyne and carbamate functionalities. Their crystalline molecular organizations have the distinctive feature of being suitable for polymerization in two potential directions, either parallel or skewed to the hydrogen-bonded (HB) network. However, single-crystal structures of the final polydiacetylenes (PDAs) demonstrate that the resulting orientation of the conjugated backbones is different for these two derivatives, which lead to HB supramolecular polymer networks (2D nanosheets) for n = 1 and to independent linear PDA chains with intramolecular HBs for n = 3. Thus, spacer length modification can be considered a new strategy to influence the molecular orientation of conjugated polymer chains, which is crucial for developing the next generation of materials with optimal mechanical and optoelectronic properties. Calculations were performed on model oligodiacetylenes to evaluate the cooperativity effect of HBs in the different crystalline supramolecular packing motifs and the energy profile related to the torsion of the conjugated backbone of a PDA chain (i.e., its ability to adopt planar or helical conformations).

更新日期：2022-04-12

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