Improved selectivity for Pb(ii) by sulfur, selenium and tellurium analogues of 1,8-anthraquinone-18-crown-5: synthesis, spectroscopy, X-ray crystallography and computational studies

Abstract

We report here a series of heteroatom-substituted macrocycles containing an anthraquinone moiety as a fluorescent signaling unit and a cyclic polyheteroether chain as the receptor. Sulfur, selenium, and tellurium derivatives of 1,8-anthraquinone-18-crown-5 (1) were synthesized by reacting sodium sulfide (Na2S), sodium selenide (Na2Se) and sodium telluride (Na2Te) with 1,8-bis(2-bromoethylethyleneoxy)anthracene-9,10-dione in a 1 : 1 ratio. The optical properties of the new compounds are examined and the sulfur and selenium analogues produce an intense green emission enhancement upon association with Pb(II) in acetonitrile. Selectivity for Pb(II) is markedly improved as compared to the oxygen analogue 1 which was also competitive for Ca(II) ion. UV-Visible and luminescence titrations reveal that 2 and 3 form 1 : 1 complexes with Pb(II), confirmed by single-crystal X-ray studies where Pb(II) is complexed within the macrocycle through coordinate covalent bonds to neighboring carbonyl, ether and heteroether donor atoms. Cyclic voltammetry of 2-8 showed classical, irreversible oxidation potentials for sulfur, selenium and tellurium heteroethers in addition to two one-electron reductions for the anthraquinone carbonyl groups. DFT calculations were also conducted on 1, 2, 3, 6, 6 + Pb(II) and 6 + Mg(II) to determine the trend in energies of the HOMO and the LUMO levels along the series.

Cyclodextrin-Based Metal-Organic Nanotube as Fluorescent Probe for Selective Turn-On Detection of Hydrogen Sulfide in Living Cells Based on H2S-Involved Coordination Mechanism

“…2a ). The time-dependent fluorescence measurements for the addition of H 2 S into the stock solution reveal that CD-MONT-2′ in DMSO exhibits rapid response toward H 2 S, which is different from the reported Pb-based complexes 29 . To further probe the fluorescence turn-on response to sulfide, various concentrations of Na 2 S (0–10 μM) were added to the stock, and the fluorescence spectra were recorded in Fig.…”

“…The design and synthesis of fluorescent turn - on probes for rapid detection of H 2 S in living cells is an active field in material chemistry and cell biology 9 17 . The development of coordination chemistry in the past decades opened a new avenue in searching fluorescent materials for selective detection of H 2 S. Actually, most of fluorescent coordination complexes including metal-organic frameworks show turn - off response towards H 2 S 29 , functional coordination complex-based probes with fluorescent turn - on response towards H 2 S are quite rare. Up to date, several MOF-based fluorescent turn - on probes have been synthesized and applied in the detection of H 2 S based on reduction/precipitation mechanism 19 .…”

Fluorescent Probes Containing Selenium as a Guest or Host

“…Chou et al 89 91 After this work, the same group developed another series of fluorescent probes for Pb 2+ detection on the basis of anthraquinone-bearing, heteroatom-substituted macrocycles (Scheme 8). 92 Probe 58 exhibits an intense green emission (l em = 520 nm, l ex = 390 nm) enhancement upon association with Pb 2+ in acetonitrile. In the process, the probe forms a 1:1 complex with Pb 2+ ions, which has been confirmed by spectroscopic titrations and X-ray crystallography.…”

“…Thus, the probe can be used to discriminate between Fe 2+ and Fe 3+ via H 2 O 2 -promoted Fenton chemistry. Furthermore, the probe can be regarded as a 2:1 multiplexing molecular logic gate in which Fe 3+ , Fe 2+ , and H 2 O 2 serve as chemical inputs.Mariappan et al91,92 developed the anthraquinone-based organoselenium probes 57 and 58 for detecting metal ions (Scheme 8). Probe 57 exhibits fluorescence enhancement upon addition of Fe 3+ and Cu 2+ because of cleavage of the aryl-oxygen ether bond.…”

Selênio e Telúrio: aplicação no desenvolvimento de novos sensores moleculares fluorescentes para detecção de cátions metálicos em meio aquoso

“…Somente em 2015 que ocorreu o primeiro relato sobre aplicação de reagentes de telúrio em sensores moleculares fluorescentes para detecção de íons metálicos. Na comunicação, Mariappan e colaboradores [43] No ano posterior, Han e colaboradores [44] [46] A existência e utilização desse metal e de seu principal minério, cinábrio (HgS), pelo ser humano, data da Grécia Antiga, onde, por ter uma aparência líquida e brilhante, era conhecido como "água prateada". [47] A obtenção de mercúrio elementar ocorre, principalmente, através do aquecimento do cinábrio em temperaturas em torno de 500-600 °C na presença de ar, onde, além do mercúrio, também é obtido dióxido de enxofre.…”