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Synthesis and Optoelectronic Properties of Janus-Dendrimer-Type Multivalent Donor–Acceptor Systems

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journal contribution
posted on 16.01.2015, 00:00 by Cagatay Dengiz, Benjamin Breiten, Jean-Paul Gisselbrecht, Corinne Boudon, Nils Trapp, W. Bernd Schweizer, François Diederich
A convergent, multistep protocol was employed for the synthesis of a Janus-type multivalent donor–acceptor system. The synthetic approach is based on a Sonogashira cross-coupling of two differently ferrocene-(Fc) substituted dendrons and a final sixfold [2 + 2] cycloaddition−retroelectrocyclization (CA−RE) reaction with tetracyanoethene, which occurs regioselectively at only one of the rigidly linked dendrons. The structural and optoelectronic properties of the compounds were investigated by X-ray analysis, UV/vis spectroscopy, and electrochemistry. The target Janus-system displays redox-amphoteric behavior. The nonalkynylated Fc end groups in one dendron are readily and reversibly oxidized. The second dendron, in which the terminal Fc-activated alkynes underwent the CA−RE reaction to give tetracyanobuta-1,3-dienes in the final step of the synthesis, undergoes four reversible 3-e reductions in the very narrow potential range of 1 V. A spontaneous intramolecular charge transfer from the donor into the acceptor hemisphere was not observed. Furthermore, the oxidation potential of the Fc donors in one hemisphere is hardly perturbed by the push–pull acceptors in the other, which suggests that electronic communication along the π-system, with several meta-connectivities, is not efficient. Therefore, the charge-transfer bands seen in the Janus-type system originate from the interaction of the Fc donors with the directly connected tetracyanobuta-1,3-diene acceptors in the same hemisphere.