Mixed‐Stack Charge Transfer Crystals of Pillar[5]quinone and Tetrathiafulvalene Exhibiting Ferroelectric Features

Ferroelectric materials find extensive applications in the fabrication of compact memory devices and ultra‐sensitive multifunctional detectors. Face‐to‐face alternate stacking of electron donors and acceptors effectuate long‐range unidirectional ordering of charge‐transfer (CT) dipoles, promising tu...

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Bibliographic Details
Published in:Chemistry : a European journal 2017-09, Vol.23 (51), p.12630-12635
Main Authors: Shivakumar, Kilingaru I., Swathi, Kadaba, Goudappagouda, Das, Tamal C., Kumar, Ashwani, Makde, Ravindra D., Vanka, Kumar, Narayan, Kavassery S., Babu, Sukumaran Santhosh, Sanjayan, Gangadhar J.
Format: Article
Language:English
Subjects:
Beryl
Charge transfer
charge-transfer complexes
Chemistry
Computed tomography
Crystals
Data storage
Detectors
Dimers
Fabrication
ferroelectric
Ferroelectric materials
macrocycles
Memory devices
Optical polarization
Phase transitions
pi-interaction
Piezoelectricity
pillarquinone
Polarization
Quinones
Single crystals
X-ray diffraction
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Summary:Ferroelectric materials find extensive applications in the fabrication of compact memory devices and ultra‐sensitive multifunctional detectors. Face‐to‐face alternate stacking of electron donors and acceptors effectuate long‐range unidirectional ordering of charge‐transfer (CT) dipoles, promising tunable ferroelectricity. Herein we report a new TTF‐quinone system‐an emerald green CT complex consisting pillar[5]quinone (P5Q) and tetrathiafulvalene (TTF). The CT crystals, as determined by single crystal synchrotron X‐ray diffraction, adopt a 1:1 mixed‐stack arrangement of donor and acceptor with alternating dimers of TTF and 1,4‐dioxane encapsulated P5Q. The TTF‐P5Q.dioxane crystal possesses a macroscopic polarization axis giving rise to ferroelectricity at room temperature. The CT complex manifests ferroelectric features such as optical polarization rotation, temperature‐dependent phase transition and piezoelectric response in single crystals. Ferroelectric behavior observed in P5Q‐based CT complex widens the scope for further work on this structurally intriguing and readily accessible cyclic pentaquinone. We alternate as dimers: Emerald‐green charge‐transfer (CT) complex of acceptor pillar[5]quinone (P5Q) and donor tetrathiafulvalene (TTF) crystallize in 1:1 mixed‐stack arrays with alternating dimers of P5Q and TTF. The CT axis is found to support switchable macroscopic polarization at room temperature.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201702577