Broad-Band Near-Infrared Doublet Emission in a Tetrathiafulvalene-Based Metal-Organic Framework.,The Journal of Physical Chemistry Letters

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Broad-Band Near-Infrared Doublet Emission in a Tetrathiafulvalene-Based Metal-Organic Framework.
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-01-16 , DOI: 10.1021/acs.jpclett.9b03383
Feifan Wang ₁ , Jue Wang ₁ , Sebastian F Maehrlein ₁ , Yingzi Ma ₁ , Fang Liu ₁ , X-Y Zhu ₁

Affiliation

The upper limit in LED quantum efficiency from conventional closed-shell molecules is 25% as dictated by singlet and triplet spin statistics. Spin-doublet organic molecules are attractive candidates to exceed this limit, thanks to their 100% theoretical quantum efficiency in radiative recombination. However, examples of stable spin-doublet molecules in the solid state are rare. Here we show broad-band near-infrared emission in the columnar π-π stacked tetrathiafulvalene (TTF) in a metal organic framework (MOF) single crystal. The broad emission is similar to known TTF+• doublet emission and is stabilized in the MOF crystal. This interpretation is supported by the observation of enhanced PL emission following UV oxidation of the MOF crystal to increase the doublet concentration. The findings suggest tetrathiafulvalene-based MOFs as promising materials for near-IR light emission and the MOF structure may be a general strategy to stabilize radical cation species in the solid state.

中文翻译：

基于四硫富瓦烯的金属有机框架中的宽带近红外双峰发射。

由单重态和三重态自旋统计表明，常规闭壳分子的LED量子效率上限为25％。由于其在辐射复合中的理论量子效率为100％，自旋双峰有机分子是超过此极限的诱人候选物。但是，固态的自旋双峰分子的实例很少。在这里，我们在金属有机骨架（MOF）单晶中的柱状π-π堆积四硫富瓦烯（TTF）中显示了宽带近红外发射。宽发射类似于已知的TTF +•双峰发射，并且在MOF晶体中稳定。观察到MOF晶体被UV氧化以增加双峰浓度后PL发射增强，从而支持了这种解释。

更新日期：2020-01-17

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