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高度共轭的2,2':6':2″-三联吡啶配合物的双发射——通向白色发光体的一条潜在途径。

Dual emission from highly conjugated 2,2':6':2″-terpyridine complexes-a potential route to white emitters.

作者信息

Siebert Ronald, Winter Andreas, Dietzek Benjamin, Schubert Ulrich S, Popp Jürgen

机构信息

Institute for Physical Chemistry, Friedrich-Schiller-University Jena, Helmholtzweg 4, 07743 Jena, Germany.

出版信息

Macromol Rapid Commun. 2010 May 12;31(9-10):883-8. doi: 10.1002/marc.200900894. Epub 2010 Mar 19.

Abstract

Here, we present a new class of terpyridine complexes of the transition-metal ions, iron(II), ruthenium(II), and osmium(II), overcoming the poor emission properties typical for this class of polypyridyl complexes. These complexes show, besides an increased room-temperature emission quantum yield and a prolonged lifetime of the metal-to-ligand charge-transfer (MLCT) states, dual emission from two well-separated excited states of the same molecule. These experimental findings are attributed to a highly stabilized ligand chromophore, where photoinduced excited-state planarization causes an enhancement of electron delocalization. This planarization, in turn, reduces the potential energy of the S(1) state and minimizes electronic coupling to the MLCT state, which is prone to non-radiative deactivation via metal-centered excited states. Due to their dual emission the complexes presented here show emission covering the entire Vis spectral range upon excitation of the ππ* states in the near UV. Thus, by structurally tuning the electronic coupling of the ππ* and the MLCT states a new synthetic route toward white emitters, which can subsequently be incorporated into polymers, is opened.

摘要

在此,我们展示了一类新型的过渡金属离子(铁(II)、钌(II)和锇(II))的三联吡啶配合物,克服了这类多吡啶配合物典型的发光性能不佳的问题。这些配合物除了具有提高的室温发射量子产率和延长的金属到配体电荷转移(MLCT)态寿命外,还从同一分子的两个充分分离的激发态发出双重发射。这些实验结果归因于高度稳定的配体发色团,其中光诱导的激发态平面化导致电子离域增强。反过来,这种平面化降低了S(1)态的势能,并使与MLCT态的电子耦合最小化,MLCT态易于通过以金属为中心的激发态进行非辐射失活。由于它们的双重发射,本文展示的配合物在近紫外光激发ππ态时,发射覆盖了整个可见光谱范围。因此,通过结构调整ππ态和MLCT态的电子耦合,开辟了一条通往白色发光体的新合成路线,随后可将其掺入聚合物中。

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