Aharon Eyal, Breuer Steffen, Jaiser Frank, Köhler Anna, Frey Gitti L
Department of Materials Engineering, Technion-Israel Institute of Technology, Haifa 32000, Israel.
Chemphyschem. 2008 Jul 14;9(10):1430-6. doi: 10.1002/cphc.200800109.
Photophysical processes in conjugated polymers are influenced by two competing effects: the extent of excited state delocalization along a chain, and the electronic interaction between chains. Experimentally, it is often difficult to separate the two because both are controlled by chain conformation. Here we demonstrate that it is possible to modify intra-chain delocalization without inducing inter-chain interactions by intercalating polymer monolayers between the sheets of an inorganic layered matrix. The red-emitting conjugated polymer, MEH-PPV, is confined to the interlayer space of layered SnS(2). The formation of isolated polymer monolayers between the SnS(2) sheets is confirmed by X-ray diffraction measurements. Photoluminescence excitation (PLE) and photoluminescence (PL) spectra of the incorporated MEH-PPV chains reveal that the morphology of the incorporated chains can be varied through the choice of solvent used for chain intercalation. Incorporation from chloroform results in more extended conformations compared to intercalation from xylene. Even highly twisted conformations can be achieved when the incorporation occurs from a methanol:chloroform mixture. The PL spectra of the MEH-PPV incorporated SnS(2) nanocomposites using the different solvents are in good agreement with the PL spectra of the same solutions, indicating that the conformation of the polymer chains in the solutions is retained upon intercalation into the inorganic host. Therefore, intercalation of conjugated polymer chains into layered hosts enables the study of intra-chain photophysical processes as a function of chain conformation.
激发态沿链的离域程度以及链间的电子相互作用。在实验中,通常很难将这两种效应区分开来,因为它们都受链构象的控制。在此我们证明,通过将聚合物单层插入无机层状基质的片层之间,可以在不诱导链间相互作用的情况下改变链内离域。红色发光共轭聚合物MEH-PPV被限制在层状SnS₂的层间空间中。通过X射线衍射测量证实了在SnS₂片层之间形成了孤立的聚合物单层。掺入的MEH-PPV链的光致发光激发(PLE)和光致发光(PL)光谱表明,通过选择用于链插层的溶剂,可以改变掺入链的形态。与从二甲苯进行插层相比,从氯仿中掺入可导致更伸展的构象。当从甲醇:氯仿混合物中进行掺入时,甚至可以实现高度扭曲的构象。使用不同溶剂的掺入了MEH-PPV的SnS₂纳米复合材料的PL光谱与相同溶液的PL光谱高度一致,这表明聚合物链在溶液中的构象在插入无机主体后得以保留。因此,将共轭聚合物链插入层状主体能够研究作为链构象函数的链内光物理过程。