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Tuning Electrical‐ and Photo‐Conductivity by Cation Exchange within a Redox‐Active Tetrathiafulvalene‐Based Metal–Organic Framework
Author(s) -
Zhou Yan,
Yu Fei,
Su Jian,
Kurmoo Mohamedally,
Zuo JingLin
Publication year - 2020
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.202008941
Subject(s) - tetrathiafulvalene , redox , chemistry , crystallinity , photocurrent , photochemistry , electron paramagnetic resonance , metal , conductivity , inorganic chemistry , materials science , crystallography , organic chemistry , molecule , optoelectronics , physics , nuclear magnetic resonance
To activate electronic and optical functions of the redox‐active metal–organic framework, (Me 2 NH 2 )[In III (TTFTB)]⋅0.7 C 2 H 5 OH⋅DMF (Me 2 NH 2 @ 1 , TTFTB=tetrathiafulvalene‐tetrabenzoate, DMF= N , N ‐dimethylformamide), has been exchanged by tetrathiafulvalenium (TTF .+ ) and N , N ′‐dimethyl‐4,4′‐bipyridinium (MV 2+ ). These cations provide electron carriers and photosensitivity. The exchange retains the crystallinity allowing single‐crystal to single‐crystal post‐synthetic transformation to TTF@ 1 and MV@ 1 . Both TTF .+ and MV 2+ enhance the electrical conductivity by a factor of 10 2 and the visible light induced photocurrent by 4 and 28 times, respectively. EPR evidences synergetic effect involving charge transfer between the framework redox‐active TTFTB bridges and MV 2+ . The results demonstrate that functionalization of MOF by cation exchange without perturbing the crystallinity extends possibilities to achieve switchable materials.