Related Experiment Video
Updated: Dec 31, 2025

A Technical Guide for Performing Spectroscopic Measurements on Metal-Organic Frameworks
Published on: April 28, 2023
Broad-Band Near-Infrared Doublet Emission in a Tetrathiafulvalene-Based Metal-Organic Framework
Feifan Wang1, Jue Wang1, Sebastian F Maehrlein1
1Department of Chemistry , Columbia University , New York , New York 10027 , United States.
Abstract:
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.
Related Concept Videos
Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
UV–Vis Spectroscopy: Molecular Electronic Transitions
Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Crystal Field Theory - Tetrahedral and Square Planar Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
IR Absorption Frequency: Delocalization
In IR...
Valence Bond Theory

