N-Triazinyl Derivatives of 1- and 9-aminoanthracene: Synthesis and Photo-Physical Properties

Abstract

New N-triazinyl derivatives were synthesized by reaction of cyanuric chloride with 1- and 9-aminoanthracenes and subsequent nucleophilic substitution of chlorine atoms on triazinyl ring with methoxy and/or phenylamino groups. The compounds were characterized by (1)H and (13)C NMR and mass spectra. The influence of the chemical structure and solvent polarity on the UV/Vis absorption and fluorescence spectra and fluorescence quantum yields were investigated. Semi-empirical computations revealed highly polar CT states in singlet excited state manifold connected with charge-transfer from the hydrocarbon moiety to the triazinyl ring. The relationships between the CT-to-emitting state energy gap, solvent polarity and fluorescence quantum yield were discussed.

Maintaining of the Green Fluorescence Emission of 9-Aminoanthracene for Bioimaging Applications

“…HCl at 0 °C to give 9-anthrylammonium chloride ( 9AAH + ·Cl – ) as a pale red solid in 84% yield (Scheme ). A solution of 9AA in MeOH exhibited an absorption band at λ max = 420 nm, which is similar to the reported values in dimethyl sulfoxide (DMSO) and CH 3 CN . The fluorescence emission of 9AA in MeOH was observed at λ max = 510 nm with a quantum yield of 19%, which was similar (20%) to that of 9AAH + ·Cl – in MeOH .…”

“…A solution of 9AA in MeOH exhibited an absorption band at λ max = 420 nm, which is similar to the reported values in dimethyl sulfoxide (DMSO) and CH 3 CN. 17 The fluorescence emission of 9AA in MeOH was observed at λ max = 510 nm with a quantum yield of 19%, which was similar (20%) to that of 9AAH + ·Cl – in MeOH a. The excitation and fluorescence spectra of 9AAH + ·Cl – observed in DMSO and MeOH have the same spectral profile and maxima as those of 9AA , whereas the fluorescence intensity of 9AAH + ·Cl – is lower than that of 9AA (see Supporting Information, Figures S-1 and S-2), thus indicating that 9AAH + ·Cl – emits green fluorescence owing to its equilibrium in solution with 9AA .…”

Novel 1- and 9-aminoanthracene/3-aminobenzanthrone bichromophores exhibiting through-bond excitation energy transfer

“…From Table 2 it is evident that ET efficiency of the studied compounds in DBE and EtAc is 88e100%. While the fluorescence quantum yields of phenylaminotriazinyl derivatives of 1-and 9-aminoathracenes are relatively high (0.2e0.5) [13], no fluorescence of the donor part was detected for bichromophores with aminobenzantronyl moiety as the acceptor. The significant fluorescence quenching in MeCN may be caused due to participation of a deactivation non-radiative process operating effectively only in a strongly polar environment.…”

“…Obtained 1.27 g (52,9%) as a red solid; mp > 300 C. 1 Ar), 7.51e7.47 (m, 1H; Ar), 3.91 ppm (br s, 3H; OCH 3 ). 13 3.4. N-(4-Methoxy-6-(3-benzanthronylamino)-1,3,5-triazin-9-yl)-9-aminoantracene (9-ATMABA).…”

“…3 and 4) overlapped absorption bands; the first broad one (425e500 nm) correspond to the absorption of N-triazinyl-3-aminobenzanthronyl moiety [12]. The second one, with clear cut vibronic structure (350e410 nm), corresponds to the absorption of N-triazinyl-aminoanthracenyl moiety [13]. The shapes of the absorption spectra and the absorption maxima of the studied compounds are similar and only a little dependent on a substituent on triazinyl ring and on solvent polarity.…”