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

Date

2015-01-16

Author

Dengiz, Çağatay
GISSELBRECHT, Jean-Paul
BOUDON, Corinne
TRAPP, Nils
SCHWEIZER, W. Bernd
DIEDERICH, Francois

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A convergent, multistep protocol was employed for the synthesis of a Janus-type multivalent donoracceptor 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 pushpull acceptors in the other, which suggests that electronic communication along the p-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.

Subject Keywords

Amphiphilic diblock dendrimers, Charge-transfer interactions, Crystal-structures, Shape-persistent, Molecular architectures, Convenient synthesis, 2+2 cycloaddition, Dendrons, Macromolecules, Chromophores

URI

https://hdl.handle.net/11511/42926

Journal

JOURNAL OF ORGANIC CHEMISTRY

DOI

https://doi.org/10.1021/jo502367h

Collections

Department of Chemistry, Article

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Citation Formats

Ç. Dengiz, J.-P. GISSELBRECHT, C. BOUDON, N. TRAPP, W. B. SCHWEIZER, and F. DIEDERICH, “Synthesis and Optoelectronic Properties of Janus-Dendrimer-Type Multivalent Donor Acceptor Systems,” JOURNAL OF ORGANIC CHEMISTRY, pp. 882–896, 2015, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/42926.