Abstract
Perylene and its derivatives are some of the most interesting chromophores in the field of molecular design. One of the most employed methodologies for their synthesis is the cyclodehydrogenation of binaphthyls mediated by Lewis acids. In this article, we investigated the cyclodehydrogenation reaction of 2-substituted binaphthyls to afford the bay-substituted perylene. By using AlCl3 as a Lewis acid and high temperatures (the Scholl reaction), two new products bearing NH2 and N(CH3)2 groups at position 2 of the perylene ring were synthesized. Under these conditions, we were also able to obtain terrylene from ternaphthalene in 38% yield after two cyclodehydrogenation reactions in a single step. The attempts to promote the formation of a radical cation (necessary intermediary for the oxidative aromatic coupling mechanism) by using FeCl3 or a strong oxidant like 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) did not yield the expected products. DFT calculations suggested that the lack of reaction for oxidative aromatic coupling is caused by the difference between the oxidation potentials of the donor/acceptor couple. In the case of the Scholl reaction, the regiochemistry involved in the formation of the σ-complex together with the activation energy of the C–C coupling reaction helped to explain the differences in the reactivity of the different substrates studied.
Highlights
In the last decades, there has been special interest in the design of speci c chromophoric structures due to their possible application in molecular devices such as light-collecting antennas and organic light emitting diodes (OLEDs), among other applications.1 Among these structures, perylene and its derivatives are interesting, since they exhibit excellent electronic and optical properties.2 Perylene shows characteristic uorescence with high quantum yield, which varies depending on both the nature of the substituents attached to the polycycle and their positions.3 Recent applications of perylene derivatives,4 include organic eld effect transistors,5 organic photovoltaic cells,6 optical switches7 and molecular wires.8Because of the importance of perylene and its derivatives, different strategies have been developed for their synthesis (Scheme 1, I–V)
The results suggest that compounds from Group 1 have lower oxidation potentials
In order to explore the scope of these reactions, we propose the synthesis of terrylene from 1,10:40,100-ternaphthalene (25), Scheme 5
Summary
There has been special interest in the design of speci c chromophoric structures due to their possible application in molecular devices such as light-collecting antennas and organic light emitting diodes (OLEDs), among other applications. Among these structures, perylene and its derivatives are interesting, since they exhibit excellent electronic and optical properties. Perylene shows characteristic uorescence with high quantum yield, which varies depending on both the nature of the substituents attached to the polycycle and their positions (e.g. the axial or equatorial regions). Recent applications of perylene derivatives (mostly perylene diimides, PDIs), include organic eld effect transistors, organic photovoltaic cells, optical switches and molecular wires.8Because of the importance of perylene and its derivatives, different strategies have been developed for their synthesis (Scheme 1, I–V). There has been special interest in the design of speci c chromophoric structures due to their possible application in molecular devices such as light-collecting antennas and organic light emitting diodes (OLEDs), among other applications.. There has been special interest in the design of speci c chromophoric structures due to their possible application in molecular devices such as light-collecting antennas and organic light emitting diodes (OLEDs), among other applications.1 Among these structures, perylene and its derivatives are interesting, since they exhibit excellent electronic and optical properties.. Because of the importance of perylene and its derivatives, different strategies have been developed for their synthesis (Scheme 1, I–V).
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