Saddle‐Shaped Cyclic Indole Tetramers: 3D Electroactive Molecules |
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Authors: | Constanza Ruiz Prof?Dr Ángeles Monge Prof?Dr Enrique Gutiérrez‐Puebla Prof?Dr Ibon Alkorta Prof?Dr José Elguero Prof Juan T López Navarrete Dr M Carmen Ruiz?Delgado Dr Berta Gómez‐Lor |
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Institution: | 1. Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, Madrid, Spain;2. Instituto de Química Médica, CSIC, Madrid, Spain;3. Department of Physical Chemistry, University of Málaga, Málaga, Spain;4. (+34)?91‐3349031 |
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Abstract: | We present a joint theoretical and experimental study of a series of cyclic indole tetramers aimed at understanding the fundamental electronic properties of this 3D platform and evaluating its potential in the construction of new semiconductors. To this end, we combined absorption and Raman spectroscopy, cyclic voltammetry, and spectroelectrochemistry with DFT calculations. Our results suggest that this platform can be easily and reversibly oxidized. Additionally, it has a HOMO that matches very well with the workfunction of gold, therefore charge injection from a gold electrode is expected to occur without significant barriers. Interestingly, the cyclic tetraindoles allow for good electron delocalization in spite of their saddle‐shaped structures. The steric constraints introduced by N‐substitution significantly inhibits ring inversion of the central cyclooctatetraene unit, whereas it only barely affects the optical and electrochemical properties (a slightly higher oxidation potential and a blueshifted absorption upon alkylation are observed). |
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Keywords: | cyclooctatetraene hyperconjugation organic semiconductors spectroelectrochemistry tetraindoles |
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