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This work presents a systematic evaluation of 2-amino, 5-amino and 2,5-diamino substituted benzimidazo[1,2-a]quinoline-6-carbonitriles as novel pH probes with a potential application in pH sensing materials or as H+ fluoroionophores in bulk optode membranes. The study was carried out by varying the length, type and position of amino substituents in ten fluorescent dyes with the same benzimidazo[1,2-a]quinoline-6-carbonitrile core. The photophysical and acid-base properties of the dyes were investigated by the UV/Vis absorption and fluorescence spectroscopies, and interpreted by the electronic structure DFT calculations. pH sensing mechanisms and structure-property relations affecting the fluorescence response were discussed through a detailed analysis of the piperidine substituted derivatives 1–4. Push–pull donor–acceptor interactions stimulate strong fluorescence in the visible spectral range (up to Φ = 0.65 for 7) and induce significant changes in the photophysical properties associated with the acid-base equilibria (up to a 50-fold increase in the fluorescence intensity). pKa values in aqueous and mixed solutions (v/v H2O:EtOH 99:1, 50:50), appear suitable for monitoring acidic pH in solution. The most promising candidates were immobilised in thin polymer matrices by the spin coating technique to form fluorescent sensing materials – optodes, and examined as novel pH-sensitive fluoroionophores. In the liquid membrane environment, dyes exhibited significant increase of the apparent pKas by almost 4 units. Bright and blue emissive thin films showed pH response and dynamic range around pKa = 5, making them suitable for a wide range of optical sensing applications.

Amide linked lower rim 1,3-dibenzimidazole derivative of calix[4]arene, L has been shown to be sensitive and selective to Hg(2+) in aqueous acetonitrile solution based on fluorescence spectroscopy, and the stoichiometry of the complexed species has been found to be 1:1. The selectivity of L toward Hg(2+) has been shown among 11 M(2+) ions, viz., Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), Ca(2+), and Mg(2+) studied, including those of the mercury group and none of these ions impede the recognition of Hg(2+) by L. Role of the solvent on the recognition of Hg(2+) has been demonstrated. The role of calix[4]arene platform and the benzimidazole moieties in the recognition of Hg(2+) by L has been delineated upon performing such studies with five different molecules of relevance as reference molecular systems. The binding cores formed by the receptor L and the reference compounds have been established based on the single crystal XRD structures, and the preferential metal ion binding cores have been discussed. The binding of Hg(2+) with L has been further established based on (1)H and (13)C NMR, ESI MS, absorption, and fluorescence lifetime measurements. Some of these techniques have been used to establish the stoichiometry of the species formed. The complex species formed between L and Hg(2+) have been isolated and characterized and found to be 1:1 species even in the isolated complex. Whereas transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM) provided the nanostructural behavior of L, the TEM and SEM demonstrated that the mercury complex has different characteristics when compared to L. The TEM, SEM, and powder XRD studies revealed that whereas L is crystalline, that of the mercury complex is not, perhaps a reason for not being able to obtain single crystals of the complex. Binding characteristics of Hg(2+) toward L have been established based on the DFT computational calculations.

International audience; Two N-pyrenylacetamide-substituted sugar-aza-crown ethers have been synthesized as new fluorescent chemosensors. The designed ligands 1 and 2 exhibit fluorescence characteristics of a pyrene monomer and a dynamic excimer emission when compared to N-pyrenylacetamide as a model compound. Both ligands displayed a Cu2+-sensitive fluorescence quenching with a 1:1 stoichiometry and high stability constants (log K = 6.7 for 1 and 7.8 for 2). The quenching effect was rationalized on the basis of photoinduced electron transfer from the excited pyrene to the complexed Cu2+ cation, while the changes in excimer-to-monomer ratio were explained by a conformational analysis through DFT calculations. The predicted structure suggests that the Cu2+ cation is coordinated with the two carbonyl groups and the sugar-aza-crown ethers which rigidified the complex structure and placed the two pyrene moieties far apart.

A pyrenyl-imino-C2-glucosyl conjugate, L, has been synthesized and characterized. The L exhibits selective chromogenic as well as fluorescent property towards Hg2+ in a ratiometric manner by showing similar to 30 fold enhanced fluorescence emission intensity. The fluorescence enhancement continues to be there even in the presence of thirteen other competitive metal ions studied. The sensing of Hg2+ is well demonstrated using various techniques, such as, fluorescence, absorption, visual color under UV light and ESI MS. A minimum detection limit of 18 +/- 2 ppb was shown by L for Hg2+ in ethanol. All the experimental studies carried out supported the formation of 2:1 complex between L and Hg2+. The structure of the 2:1 complex was modeled at ab initio using HF and found a structure where Hg2+ is sandwiched between the two pyrenyl moieties. The reversibility and reusability of L has been demonstrated using fluoride ion. (C) 2014 Elsevier Ltd. All rights reserved.

Keywords: fluorescence ; metallacrown complexes ; ruthenium ; self-assembly ; sensors ; Supramolecular Triangular Hosts ; Organometallic Receptors ; Selective Extraction ; Crown-Ethers ; Complexes ; Li+ ; Sensor ; Recognition ; Fluoroionophore ; Ionophore Reference EPFL-ARTICLE-148459doi:10.1002/chem.200903119View record in Web of Science Record created on 2010-04-23, modified on 2017-05-12

Fluorescent dihydroxypyridine ligands were prepared by attaching pyrene-, dansyl-, and methoxycoumarin-fluorophores via dimethyleneamine linkers. The reaction of these ligands with [(p-cymene)RuCl(2)](2) or [(C(6)H(5)CH(2)NMe(2)H)RuCl(2)](2)Cl(2) resulted in the formation of 12-metallacrown-3 complexes, which possess strong affinity for lithium ions. By a judicious choice of the fluorophore and the arene pi-ligand, a macrocycle was obtained that could be used in aqueous solution to selectively and quantitatively detect lithium ions by fluorescence spectroscopy.