Macromolecular Effect Stabilized Color-Tunable and Room Temperature Charge-Transfer Complexes Based on Donor–Acceptor Assemblies,ACS Applied Polymer Materials

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Macromolecular Effect Stabilized Color-Tunable and Room Temperature Charge-Transfer Complexes Based on Donor–Acceptor Assemblies
ACS Applied Polymer Materials ( IF 4.4 ) Pub Date : 2020-02-12 , DOI: 10.1021/acsapm.9b00917
Karnati Narasimha ₁

Affiliation

We report one of the first examples of room temperature stable solid-state charge transfer (CT) complexes based on a segmented π-conjugated polymer and rylene diimide donor–acceptor system having tunable optical transitions from the visible to NIR region in the solar spectrum. Semicrystalline and amorphous segmented oligo-phenylenevinylene (OPV) chromophore containing polymers were tailor-made with flexible polymethylene chains in the backbone. The electron rich segmented OPV polymers were complexed with two electron-deficient diimides based on naphthalene (NDI) and phenylene (PDI) core. The binary complexes of segmented OPV polymers and rylene diimides produced unique classes of CT complexes based on OPV-NDI and OPV-PDI chromophore diads. Electron microscope, polarizing microscope, and X-ray diffraction analyses provided direct evidence for the two-dimensional lamellar packing of D–A self-assembly in the solid state. Detailed absorption and emission photophysical studies revealed that the donor OPV polymers and acceptor chromophores exhibited a 1:1 complex with respect to the long-range order of D–A–D–A–D–A π-stacked supramolecular assemblies. The role of the macromolecular effect on the CT complexation was further investigated using structurally identical OPV monomers. The monomer OPV-NDI complexes (or PDI complexes) were found to exhibit CT complex in the solution; however, they underwent uncontrollable phase separation into their individual D and A crystalline domains and lost their CT self-assembly in the solid state. Interestingly, the macromolecular effect driven supramolecular self-organization of long chain segmented OPV polymers produced stable CT complexes both in solution and solid state under ambient conditions. Segmented OPV polymer + PDI and segmented OPV polymer + NDI complexes were produced as red and green colored CT complexes, respectively. This enabled the accomplishment of room temperature stable CT complexes in π-conjugated polymers having absorption ranging from 350 to 1100 nm. These donor–acceptor CT self-assemblies are processable into thin films under solvent free melt crystallization process; thus, the present segmented polymer design strategy opens up a platform for donor–acceptor CT complexes.

中文翻译：

基于供体-受体组装的大分子效应稳定的颜色可调和室温电荷转移复合物

我们报告了基于分段π共轭聚合物和二甲苯二酰亚胺供体-受体系统的室温稳定固态电荷转移（CT）配合物的第一个例子，该系统具有从可见光谱到太阳光谱的NIR可调的光学跃迁。含有聚合物的半结晶和无定形链段低聚亚苯基亚乙烯基（OPV）发色团是量身定制的，主链上带有柔性多亚甲基链。富电子链段的OPV聚合物与两个基于萘（NDI）和亚苯基（PDI）核的缺电子二酰亚胺复合。基于OPV-NDI和OPV-PDI发色团二元体，分段的OPV聚合物和萘二甲酰亚胺的二元络合物产生了独特的CT络合物类。电子显微镜，偏光显微镜，X射线衍射分析为固态D–A自组装的二维层状堆积提供了直接证据。详细的吸收和发射光物理研究表明，相对于D–A–D–A–D–Aπ堆叠的超分子组装体的远距离顺序，施主OPV聚合物和受体发色团表现出1：1的络合物。使用结构相同的OPV单体进一步研究了高分子效应对CT络合的作用。发现单体OPV-NDI配合物（或PDI配合物）在溶液中显示出CT配合物。但是，它们经历了无法控制的相分离，进入了各自的D和A晶域，并且在固态下失去了CT自组装。有趣的是大分子效应驱动长链段式OPV聚合物的超分子自组织在环境条件下在溶液和固态下均能产生稳定的CT复合物。分段的OPV聚合物+ PDI和分段的OPV聚合物+ NDI配合物分别以红色和绿色CT配合物形式生产。这使得能够在吸收范围为350至1100nm的π-共轭聚合物中实现室温稳定的CT络合物。这些供体-受体CT自组装体可在无溶剂熔融结晶过程中加工成薄膜。因此，目前的分段聚合物设计策略为供体-受体CT复合物打开了一个平台。分段的OPV聚合物+ PDI和分段的OPV聚合物+ NDI配合物分别以红色和绿色CT配合物形式生产。这使得能够在吸收范围为350至1100nm的π-共轭聚合物中实现室温稳定的CT络合物。这些供体-受体CT自组装体可在无溶剂熔融结晶过程中加工成薄膜。因此，目前的分段聚合物设计策略为供体-受体CT复合物打开了一个平台。分段的OPV聚合物+ PDI和分段的OPV聚合物+ NDI配合物分别以红色和绿色CT配合物形式生产。这使得能够在吸收范围为350至1100nm的π-共轭聚合物中实现室温稳定的CT络合物。这些供体-受体CT自组装体可在无溶剂熔融结晶过程中加工成薄膜。因此，目前的分段聚合物设计策略为供体-受体CT复合物打开了一个平台。

更新日期：2020-02-13

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