Elsevier

Dyes and Pigments

Volume 168, September 2019, Pages 219-227
Dyes and Pigments

2,7-Disubstituted 1,3,6,8-tetraazabenzopyrenes: Synthesis, characterization, optical and electrochemical properties

https://doi.org/10.1016/j.dyepig.2019.04.062Get rights and content

Highlights

  • Reaction of guanidine with 1,4-diiodoanthraquinone leads to 2,7-diamino-1,3,6,8-tetraazabenzopyrene.

  • 2,7-Diamino-1,3,6,8-tetraazabenzopyrene is promising precursors for further functionalization.

  • Chlorine atoms in 1,3,6,8-tetraazabenzopyrenes are good leaving groups for reactions with nucleophiles.

Abstract

The syntheses of 2,7-diamino-1,3,6,8-tetraazabenzopyrene framework was achieved through CuI-catalyzed double annulation of 1,4-diiodoanthraquinone with guanidine. In addition, the preparation of series of 2,7-disubstituted 1,3,6,8-tetraazabenzopyrenes functionalized by NR2, Cdouble bondO, Cl, alkoxy and phenoxy groups with good yields was achieved through the simple transformations such as diazotization, alkylation and nucleophilic aromatic substitution. The properties of 1,3,6,8-tetraazabenzopyrenes synthesized were studied by DFT-calculations, optical and photoluminescence spectroscopy, cyclic voltammetry and light-induced EPR spectroscopy. The luminescence of amino derivatives is quenched in acidic solutions depending on the degree of protonation.

Introduction

Conjugated polycyclic molecules are extensively used for development of functional organic materials [1,2]. The polycyclic aromatic hydrocarbons (PAHs) are among the most investigated classes of promising compounds for application as charge transport materials [[3], [4], [5]], light-emitters [6], and active moieties of fluorescent probes [7,8]. In particular, pyrene derivatives were used as luminophores for biochemical research [9,10], as chemosensors for detection of various compounds [11] and as semiconductors [12] for organic field-effect transistors [13,14] and light-emitting diodes [15,16].

Polycyclic N-heteroaromatic compounds (N-PAHs) are equally attractive for application in materials science [17]. In fact, N-PAHs, similarly to PAHs, can be used as chromophores, chemosensors and semiconductors [[18], [19], [20]]. The significant effect of heteroatoms on electronic and optical properties as well as, on stability of the material was previously reported [[21], [22], [23]]. In addition, conjugated frameworks containing nitrogen atoms show some extra properties as compared to the corresponding hydrocarbons. For example, electron-deficient heterocycles are more prone to n-type charge transport while PAHs are typically p-type semiconductors [[24], [25], [26], [27], [28]].

Meanwhile, due to limited synthetic accessibility of N-PAHs they are less studied than PAHs. Therefore, the development of synthetic approaches to N-PAHs attracts attention of researchers. Notable examples of peri-fused N-PAHs are aza- and poliazapyrenes, which are promising luminescent materials [[29], [30], [31], [32]] and also known in the dyestuff industry as anthraquinone dyes [33,34]. For some azapyrenes with different numbers and positions of nitrogen atoms, including ring-fused derivatives, synthetic routes were previously developed [[35], [36], [37]]. However, the precedents of preparing their fused derivatives are rare [29,38]. Meanwhile, the size of the conjugated polycyclic system plays an important role for most functional materials [1,2].

Previously, we have reported a simple approach to synthesize substituted 1,3,7,9-tetraazaperylene derivatives [39]. The advantage of our approach is one stage assembly of tetraazaperylene core by double peri-condensation of guanidine with 1,5-diiodoanthraquinone in Ullmann conditions. In this work, we report a similar route to synthesize substituted 1,3,6,8-tetraazabenzopyrene derivatives (see Scheme 1, Scheme 2). Additionally, 2,7-diamino-1,3,6,8-tetraazabenzopyrene obtained was functionalized by facile transformations into derivatives containing various sets of substituents (Cl, OAlk, OPh) including auxochromes (NR2). The optical, photoluminescent (PL), and electrochemical properties of the compounds synthesized were evaluated.

Section snippets

General

Elemental analyses were performed with a CHN-analyzer (Model 1106, ‘Carlo Erba’, Italy). The 1H and 13C NMR spectra were recorded on a Bruker AV-500 spectrometer. Melting points were determined with a 1101D Mel-Temp Digital Melting Point apparatus (Electrothermal). Mass spectra were measured on a Thermo Electron Corporation DFS mass spectrometer (70 eV) using direct injection, the temperature of the ionization chamber was 220–270 °C. Cyclic voltammetry measurements were performed in CH2Cl2

Synthesis and characterization

Previously, we demonstrated the application of the reaction of guanidine with iodo-anthraquinones for the synthesis of benzoperimidines [47] and tetraazaperylenes [39]. Tetraazabenzopyrenes are another variant of the pentacyclic peri-condensed system, which can be obtained by our approach. In this case, 1,4-diiodoanthraquinone was used as the starting compound, while the other conditions remained the same. Namely, the condensation of two guanidine molecules with 1,4-diiodoanthraquinone in

Conclusions

Double condensation of guanidine with 1,4-diiodoanthraquinone is a simple and effective approach to the assembly of the tetraazabenzopyrene framework. The polycondensed product contains two amino groups, therefore it easily transforms into new promising precursors. In the case of diazotization of diamine, anthradipyrimidone is formed, which is a convenient substrate for functionalization. Selective O-alkylation of anthradipyrimidone with octyl bromide leads to dialkoxy derivative. The potential

Acknowledgments

This work was supported by the Russian Foundation for Basic Research (grant number 16-03-00082 and 18-43-540007).

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