Kim Youngmi, Bouffard Jean, Kooi Steven E, Swager Timothy M
Department of Chemistry and Institute for Soldier Nanotechnologies, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
J Am Chem Soc. 2005 Oct 5;127(39):13726-31. doi: 10.1021/ja053893+.
Conjugated polymers often display a decrease of fluorescence efficiency upon aggregation due in large part to enhanced interpolymer interactions that produce weakly emissive species generally described as having excimer-like character. We have found that poly(phenylene ethynylene)s with fused pendant [2.2.2] ring structures having alkene bridges substituted with two ester groups function to give highly emissive, broad, and red-shifted emission spectra in the solid state. To best understand the origin of this new solid-state emissive species, we have performed photophysical studies of a series of different materials in solution, spin-coated thin films, solid solutions, and Langmuir films. We conclude that the new, red-shifted, emissive species originate from excimers produced by interchain interactions being mediated by the particular [2.2.2] ring system employed. The ability to design structures that can reliably produce highly emissive conjugated polymer excimers offers new opportunities in the emission tailoring of electroluminescence and sensory devices.
共轭聚合物在聚集时通常会表现出荧光效率的降低,这在很大程度上归因于增强的聚合物间相互作用,这种相互作用产生了通常被描述为具有类准分子特征的弱发射物种。我们发现,具有稠合侧基[2.2.2]环结构且烯烃桥被两个酯基取代的聚亚苯基乙炔在固态下能产生高发射、宽且红移的发射光谱。为了更好地理解这种新型固态发射物种的起源,我们对一系列不同材料在溶液、旋涂薄膜、固溶体和朗缪尔膜中的光物理性质进行了研究。我们得出结论,这种新的、红移的发射物种源自由所采用的特定[2.2.2]环系统介导的链间相互作用产生的准分子。设计能够可靠地产生高发射共轭聚合物准分子的结构的能力,为电致发光和传感设备的发射定制提供了新的机会。