Synthesis and Electrochemical and Photophysical Properties of Azaterrylene Derivatives

Abstract

As eries of terrylene derivatives, such as monoazaterrylene (MATe rry), 1,6-diazaterrylene (DiATe rry) and pristine terrylene (Terry), were synthesized by changing the number of nitrogen atoms at the bay region (1 and 6p ositions of the Terry core). The electrochemical measurements suggested that the first one-electronreductionand oxidation potentials becamep ositivelys hifted with increasing numberso f nitrogen atoms. This agreedw ith the energies of the corresponding highest occupied molecularo rbital (HOMO) and lowest unoccupied molecular orbital (LUMO) states estimated by DFT methods. In contrast, the HOMO-LUMO gaps ap-proximately remained constant. This trend is quite similart o the spectroscopicb ehaviors observed by absorption and fluorescences pectra. The solvent polarity-dependent spectroscopic trends of DiATerry suggested the intramolecular charge-transfer (ICT) characters. Thee valuation of the excited-state dynamics in variouss olvents indicated the electronic configurational changes of the excited states relative to the ground state via the ICT.T his was supported by the Lippert-Matagap lots. Finally, the reversible protonation and deprotonation processes were also observed.

Benzo[de]naphtho[1,8-gh]quinolines: synthesis, photophysical studies and nitro explosives detection

“…Thus, the starting isoquinoline 1 was kept in a solution of dry toluene at 95 °C in the presence of metallic potassium for 6 h (Scheme 1). The yields of mono-and dimethoxy-substituted azaperylenes 5 were 33% and 11%, respectively, which is acceptable for reactions of this type [6,11]. The obtained azaperylenes 5 demonstrated promising photophysical properties.…”

“…Meanwhile, the introduction of a pyridine nitrogen atom into the structure of polycyclic aromatic hydrocarbons can be useful for creating more efficient chemosensors by combining π-excess receptor and fluorophore fragments into one molecule and enhancing the receptor properties, for example, in relation to nitro-analytes, by creating π-conjugated donor-acceptor ensembles [1]. It should be noted that aza analogs of perylene often have promising fluorescent characteristics, as well as higher LUMO energies values, which may determine the greater ability of azaperylenes to detect nitro explosives, including aliphatic ones [6,7].…”

New naphtho[1,8-ef]perimidines: synthesis, fluorescence studies and application for detection of nitroanalytes

“…The method of intramolecular cyclization [13], according to which the quinazoline 3 was kept in a solution of dry toluene at 95 °C in the presence of potassium for 6 h, was more successful. The yield of12-methoxynaphtho[1,8-ef]perimidine 4 after purification by column chromatography was 16%, which is acceptable for reactions of this type [8,13]. In addition, 12-oxonaphto[1,8-ef]pyrimidine 5 was similarly obtained from quinazoline 1 in 18% yield.…”

“…Among currently known poly(hetero)aromatic fluorophores, di-, triand tetraazaperylenes possess the most promising photophysical properties. At the same time, they have higher LUMO energies values, which in turn may provide better detection capability, for example, for aliphatic nitrocontaining explosives [8,9]. However, no examples of using azaperylenes as chemosensors for such nitro analytes have been described in the literature so far.…”

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

“…Cyclizations of naphthyl-, azanaphthyl-, or 2,7-naphthyridinyl-substituted perylenes 48.1a – c were reported by Hasobe and co-workers to produce terrylenes 48.2a – c ( Scheme 48 ). 80 Oxidative coupling conditions were used for the naphthyl-containing substrate 48.1a ; this approach is however known to fail with electron-deficient N - doped compounds. Thus, cyclization of 48.1b – c was performed under the radical anion coupling conditions (CR2017, Section 3.1 ), i.e., via treatment with potassium in xylene followed by air bubbling (cf.…”