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Saddle‐Shaped Cyclic Indole Tetramers: 3D Electroactive Molecules
Author(s) -
Ruiz Constanza,
Monge Ángeles,
GutiérrezPuebla Enrique,
Alkorta Ibon,
Elguero José,
Navarrete Juan T. López,
Ruiz Delgado M. Carmen,
GómezLor Berta
Publication year - 2016
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.201600932
Subject(s) - cyclic voltammetry , indole test , delocalized electron , chemistry , raman spectroscopy , steric effects , cyclooctatetraene , molecule , sn2 reaction , photochemistry , crystallography , electrochemistry , computational chemistry , chemical physics , electrode , stereochemistry , organic chemistry , physics , optics
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).