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Three Ni(ii)-POCOP pincer complexes [NiCl{CH-4-OH-2,6-(OPPh)}], 1; [NiCl{CH-4-OH-2,6-(OPtBu)}], 2 and [NiCl{CH-4-OH-2,6-(OPiPr)}], 3 were studied as bifunctional molecular sensors for inorganic anions and acetate. In CHCN, fluoride generates a bathochromic shift with a colorimetric change for 1-3 with a simultaneous fluorescence turn on, this optical effect is based on deprotonation of the para-hydroxy group of the POCOP ligand. On the other hand, in a neutral aqueous solution of 80 vol% CHCN, additions of cyanide produce a distinct change of color by forming very stable complexes with the nickel-based receptors 1-3 with log K in the range of 4.38-5.03 M and pronounced selectivity over other common anions such as iodide, phosphate, and acetate. Additionally, bromide shows a modest spectral change and affinity, but lower than those observed for cyanide. On the basis of H NMR experiments, UV-vis titrations, ESI-MS experiments, and the crystal structure of the neutral bromo complex of 1, it is proposed that the colorimetric change involves an exchange of chloride by CN on the Ni(ii) atom. The Ni(ii)-based sensor 1 allows the fluorescent selective detection of fluoride with a limit of 5.66 μmol L and colorimetric sensing of cyanide in aqueous medium in the micromolar concentration range.

Three new diboronic acid-substituted bisquinolinium salts were synthesized, structurally described by single-crystal X-ray diffraction, and studied in-depth as fluorescent receptors for six monosaccharides and two open-chain polyols in water at physiological pH. The dicationic pyridine-2,6-dicarboxamide-based receptors contain two N-quinolinium rings as the fluorescent units covalently linked to three different isomers of phenylboronic acid (ortho, 2; meta, 3; and para, 4) as chelating binding sites for polyols. Additions of glucose/fructose in the micromolar concentration range to receptors 2 and 3 induce significant fluorescence changes, but in the presence of arabinose, galactose, mannose, and xylose, only modest optical changes are observed. This optical change is attributed to a static photoinduced electron transfer mechanism. The meta-diboronic receptor 3 exhibited a high affinity/selectivity toward glucose (K = 3800 M −1 ) over other monosaccharides including common interfering species such as fructose and mannitol. Based on multiple spectroscopic tools, electrospray ionization high-resolution mass spectrometry, crystal structures, and density functional theory calculations, the binding mode between 3 and glucose is proposed as a 1:1 complex with the glucofuranose form involving a cooperative chelating diboronate binding. These results demonstrate the usefulness of a new set of cationic fluorescent diboronic acid receptors with a strong ability for optical recognition of glucose in the sub-millimolar concentration range.

Biological catecholamines such as L-DOPA and dopamine play vital physiological roles in brain, and are chemical indicators of human diseases. A new range of fluorescent Zn(II)-terpyridine complexes are described and...

Guanosine triphosphate (GTP) is a key biomarker of multiple cellular processes and human diseases. The new fluorescent dinuclear complex [Zn 2 (L)(S)][OTf] 4 , 1 (asymmetric ligand, L = 5,8-Bis{[bis(2-pyridylmethyl)amino] methyl}quinoline, S = solvent, and OTf = triflate anion) was synthesized and studied in-depth as a chemosensor for nucleoside polyphosphates and inorganic anions in pure water. Additions at neutral pH of nucleoside triphosphates, guanosine diphosphate, guanosine monophosphate, and pyrophosphate (PPi) to 1 quench its blue emission (λ em = 410 nm) with a pronounced selectivity toward GTP over other anions, including adenosine triphosphate (ATP), uridine triphosphate (UTP), and cytidine triphosphate (CTP). The efficient quenching response by the addition of GTP was observed in the presence of coexisting species in blood plasma and urine with a detection limit of 9.2 μmol L −1 . GTP also shows much tighter binding to the receptor 1 on a submicromolar level. On the basis of multiple spectroscopic tools ( 1 H, 31 P NMR, UV−vis, and fluorescence) and DFT calculations, the binding mode is proposed through three-point recognition involving the simultaneous coordination of the N 7 atom of the guanosine motif and two phosphate groups to the two Zn(II) atoms. Spectroscopic studies, MS-ESI, and DFT suggested that GTP bound to 1 in 1:1 and 2:2 models with high overall binding constants of log β 1 (1:1) = 6.05 ± 0.01 and log β 2 = 10.91 ± 0.03, respectively. The optical change and selectivity are attributed to the efficient binding of GTP to 1 by the combination of a strong electrostatic contribution and synergic effects of coordination bonds. Such GTP selectivity of an asymmetric metal-based receptor in water is still rare.

A dicationic pyridine-2,6-dicarboxamide-based compound 1 bearing two N-alkylquinolinium units was synthesized, determined by single-crystal X-ray diffraction, and studied as a fluorescent receptor for nucleotides and inorganic phosphorylated anions in pure water.

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