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A Divalent Pentastable Redox‐Switchable Donor–Acceptor Rotaxane
Author(s) -
Schröder Hendrik V.,
Hupatz Henrik,
Achazi Andreas J.,
Sobottka Sebastian,
Sarkar Biprajit,
Paulus Beate,
Schalley Christoph A.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605710
Subject(s) - rotaxane , homo/lumo , chemistry , tetrathiafulvalene , acceptor , redox , intramolecular force , photochemistry , cyclic voltammetry , divalent , crystallography , stereochemistry , electrochemistry , supramolecular chemistry , inorganic chemistry , molecule , crystal structure , organic chemistry , electrode , physics , condensed matter physics
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.