A Divalent Pentastable Redox‐Switchable Donor–Acceptor Rotaxane

Donor–acceptor materials with small HOMO–LUMO gaps are important in molecular electronics, but are often difficult to synthesise. A simple and efficient way to position tetrathiafulvalene (TTF) as the donor and naphthalene diamide (NDI) as the acceptor in close proximity to each other in a divalent...

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Bibliographic Details
Published in:Chemistry : a European journal 2017-02, Vol.23 (12), p.2960-2967
Main Authors: Schröder, Hendrik V., Hupatz, Henrik, Achazi, Andreas J., Sobottka, Sebastian, Sarkar, Biprajit, Paulus, Beate, Schalley, Christoph A.
Format: Article
Language:English
Subjects:
Brick
Chemistry
Cycloaddition
donor–acceptor systems
Mathematical analysis
molecular devices
Molecular electronics
multivalency
Optoelectronics
Proximity
redox chemistry
Rotaxanes
Self assembly
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Summary:Donor–acceptor materials with small HOMO–LUMO gaps are important in molecular electronics, but are often difficult to synthesise. A simple and efficient way to position tetrathiafulvalene (TTF) as the donor and naphthalene diamide (NDI) as the acceptor in close proximity to each other in a divalent crown/ammonium pseudo[2]rotaxane is presented. The divalent design provides high chelate cooperativity and much stronger binding compared with a monovalent analogue. The pseudo[2]rotaxane was then doubly interlocked by stoppering it in a catalyst‐free 1,3‐dipolar cycloaddition. UV/Vis and cyclic voltammetry experiments with the resulting [2]rotaxane revealed the optoelectronic properties of an intramolecular charge transfer with a small HOMO–LUMO energy gap. Redox‐switching experiments showed the rotaxane to be pentastable. DFT calculations provided insights into the electronic structures of the five redox states. Click the brick: Donor–acceptor materials are important for molecular electronics. A straightforward multivalent self‐assembly approach is presented, in which donor and acceptor units are “clicked” together like building bricks to force their spatial proximity (see figure). Emergent optoelectronic properties and electrochemical switching were investigated and are supported by theoretical calculations.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201605710