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Persistent Radical Tetrathiafulvalene‐Based 2D Metal‐Organic Frameworks and Their Application in Efficient Photothermal Conversion
Author(s) -
Su Jian,
Xu Ning,
Murase Ryuichi,
Yang ZhiMei,
D'Alessandro Deanna M.,
Zuo JingLin,
Zhu Jia
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202013811
Subject(s) - tetrathiafulvalene , trimer , delocalized electron , chemistry , radical , thermal stability , unpaired electron , photochemistry , x ray photoelectron spectroscopy , intramolecular force , electron paramagnetic resonance , metal organic framework , absorption (acoustics) , crystallography , materials science , molecule , dimer , organic chemistry , nuclear magnetic resonance , adsorption , composite material , physics
Abstract A series of stable radical 2D metal‐organic frameworks has been assembled. ( m ‐TTFTB) 3 ( m ‐Tetrathiafulvalene‐tetrabenzoate) trimer building blocks are beneficial for the stability of the radicals due to delocalization of the unpaired electron. Hexanuclear rare‐earth‐cluster‐based 1D chains further enhance the stability of the frameworks. The radical state of the middle TTF in the trimer has been observed by the change of central C−C and C−S bond distances and the configuration of the TTF by single‐crystal X‐ray diffraction. The radical characteristics are also confirmed by electron paramagnetic resonance, UV/Vis–NIR absorption, and X‐ray photoelectron spectroscopy experiments. Stability tests showed that the radicals are stable even in solutions and under acid/base environments (pH 1–12). Owing to efficient light absorption due to intramolecular charge transfer, low thermal conductivity, and outstanding stability, the radical 2D Dy‐MOF shows excellent photothermal properties, an increase of 34.7 °C within 240 s under one‐sun illumination.