Synthesis, Structural Characterization, Experimental, and Computational Spectrophotometric Studies of 8-Quinolinyloxymethyphosphonate Compounds

Abstract

The synthesis of diethyl-8-quinolinyloxymethylphosphonate 1 and 8-quinolinyloxymethylphosphonic acid hemihydroiodide 2 is reported along with their spectroscopic and analytical characteristics (NMR, infrared, mass spectra, and elemental analysis). The single-crystal X-ray structure of 2 is described. Solutions of the disodium phosphonate 3, from 2 and sodium hydroxide, were prepared and used in situ. The coordination complex between 1 and zinc chloride 4 is described according to its single-crystal X-ray structure. The spectrophotometric features (absorption and emission) of 1, 2, 3, and 4 are reported along with the fluorescence response and affinity of 3 to some metal cations. The origin of the fluorescence from compounds 1 and 4 is investigated using density functional theory and the oscillator strength for each transition is computed. Two deactivation pathways, one of which is only weakly emissive, are identified in 4. In contrast to 4, which is only moderately more emissive than 1 a strong zinc-activated fluorescence response is observed from aqueous solutions of 3.

Hydrogen-bonded layers directed by the [3-O3S–C6H4–PO3H]2−dianion:catena-poly[[silver(I)-μ-4,4′-bipyridine-κ2N:N′] 3-[hydroxy(oxido)phosphinoyl]benzenesulfonate trihydrate] andcatena-poly[[[tetraaquacobalt(II)]-μ-4,4′-bipyridine-κ2N:N′] 3-[hydroxy(oxido)phosphinoyl]benzenesulfonate]

“…This is a unique arrangement, with the most similar example being seen in diprotonated -PO 3 H À groups (see, for example, Clarke et al, 2005). It is noted that symmetrical hydrogen bonds and hydrogen-bonded dimers with similar dimensions of other phosphonic acids have been reported previously (Sharma & Clearfield, 2000a,b;Bowes et al, 2003;Man et al, 2006;Courtney et al, 2006;Latham et al, 2007). The dimer is further stabilized by extensive hydrogen bonding with solvent water molecules, using one -PO 3 H À and two sulfonate O atoms as acceptors (Table 2).…”

Combined approach to uv-vis study of 2-allyl and 2-ethylthioquinolines in various solutions

“…In work [4] along with comprehensive experimental research of benzodithiazol derivatives the calculations of electron density were performed, as well as of spectra and reaction activity of the synthesized substances, which proved to be consistent with the measured data. In [5] with the help of calculations the changing of fluorescence ability of phosphonate derivatives of 8-oxyquinoline and their complexes with zinc was explained. It should be noted that functional B3LYP [6,7] and all-electron basis sets of 6-311G family [8,9] are most frequently used at present for characterization of organic molecules.…”

Phosphonates containing 8-hydroxyquinoline moiety and their metal complexes: structures, fluorescent and magnetic properties

“…So far, 8-quinolinyloxymethylphosphonic acid has been synthesized by D. M. Benoit and A. Sullivan through the phosphonomethylation of 8-hydroxyquinoline at the hydroxyl position, showing pH-dependent UV-vis and fluorescence spectra. 9 The other examples are four isostructural layered compounds reported by us, namely Ln(5pm8hqH 3 )(C 2 O 4 ) 1.5 (H 2 O)•2H 2 O [Ln(III) = Eu, Gd, Tb, Dy] (5pm8hqH 3 = 5-phosphonomethyl-8-hydroxyquinoline, Scheme 1), showing ligand-centered emissions and Ln(III)-centered emissions for the Eu(III) and Dy(III) compounds. 10 In our recent work, we further studied 5pm8hqH 3 with several aims, including (i) the influence of its solid-state structure on the luminescent property, (ii) both the structures and properties of transition-metal phosphonates based on 5pm8hqH 3 , (iii) the modification at the hydroxyl group position by a -CH 2 COOH group to obtain new metal phosphonates with interesting structures and properties.…”