Broad-Band Near-Infrared Doublet Emission in a Tetrathiafulvalene-Based Metal–Organic Framework

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.