Pressure-Induced Solid-State Polymerization of Optically-Tunable Diphenyl-Substituted Diacetylene,ACS Applied Polymer Materials

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Pressure-Induced Solid-State Polymerization of Optically-Tunable Diphenyl-Substituted Diacetylene
ACS Applied Polymer Materials ( IF 4.4 ) Pub Date : 2019-11-15 , DOI: 10.1021/acsapm.9b00732
Wan Si Tang ₁ , Timothy A. Strobel ₁

Affiliation

Solid-state topochemical polymerization (SSTP) requires well-defined geometries and space symmetries between the starting monomers and resulting polymer, and diacetylenes are excellent precursors, reacting through a 1,4-addition mechanism. The hydrocarbon molecule 1,4-diphenyl-1,3-butadiyne (DPB) has a four-carbon chain with alternating triple/single bonds, capped on each end with a phenyl group, i.e. centrosymmetric with unsaturated π-bonding characteristics. To fully realize its potential for photocatalytic applications, improved control over the assembly process is desirable to form well-ordered poly(diphenylbutadiyne) (PDPB). Here, it is shown that with increasing pressure, DPB undergoes a series of solid-state chemical reactions while maintaining crystalline order related to the starting monomeric structure. Quenchable PDPB compounds begin forming at ca. 5 GPa, which exhibit optically-tunable absorbance and photoluminescence that is controllable through the extent of compression. Above ca. 15 GPa, the system transforms into a nonhexagonally-packed crystalline array with mixed sp²/sp³ character. These stepwise changes with compression are irreversible in nature, as observed by in situ diffraction and spectroscopic methods. For the first time, the simple SSTP synthesis route allows well-aligned DPB molecules to directly transform into a PDPB material via self-assembly solely through pressure generation within a diamond anvil cell without the traditional use of catalysts, temperature, radiation, templates, or solvents.

中文翻译：

光可调二苯基取代的二乙炔的压力诱导固态聚合

固态拓扑化学聚合（SSTP）要求起始单体与所得聚合物之间具有明确定义的几何形状和空间对称性，并且二乙炔是出色的前体，可通过1,4-加成机理进行反应。烃分子1，4-二苯基-1，3-丁二炔（DPB）具有带有交替的三键/单键的四碳链，在四末端具有苯基基团，即具有不饱和π键特性的中心对称。为了完全实现其在光催化应用中的潜力，需要对组装过程进行改进的控制以形成有序的聚二苯基丁二炔（PDPB）。在此表明，随着压力的增加，DPB进行了一系列固态化学反应，同时保持了与起始单体结构有关的结晶顺序。可淬火的PDPB化合物大约在大约30℃开始形成。5 GPa，表现出光学可调的吸光度和光致发光，可通过压缩程度来控制。以上。15 GPa，系统转变为具有混合sp的非六方堆积晶体阵列² / sp ^3个字符。如通过原位衍射和光谱法观察到的，这些随着压缩的逐步变化本质上是不可逆的。首次，简单的SSTP合成路线允许排列良好的DPB分子仅通过在金刚石砧室中产生压力而通过自组装直接将其直接转化为PDPB材料，而无需传统地使用催化剂，温度，辐射，模板或溶剂。

更新日期：2019-11-15

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