A Divalent Pentastable Redox-Switchable Donor-Acceptor Rotaxane

作者：Schroeder Hendrik V; Hupatz Henrik; Achazi Andreas J; Sobottka Sebastian; Sarkar Biprajit; Paulus Beate; Schalley Christoph A

来源：Chemistry - A European Journal, 2017, 23(12): 2960-2967.

DOI：10.1002/chem.201605710

• donor-acceptor systems
• molecular devices
• multivalency
• redox chemistry
• rotaxanes

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.

• 出版日期2017-2