Photophysical Properties of New Terbium (III) Organophosphonates

This paper reports on the synthesis, characterization and photophysical properties of the Tb³⁺ organophosphonates, TbH(O₃PR)₂, methylphosphonate (R=CH₃), ethylphosphonate (R=C₂H₅), propylphosphonate (R=C₃H₇), and phenylphosphonate (R=C₆H₅). The layered Tb³⁺ organophosphonates were characterized by X-ray diffraction, IR spectroscopy, TG and elemental analysis. The interlayer distances of the Tb³⁺ organophosphonates evaluated by the X-ray diffractogram were 9.50 Å for TbH(O₃PCH₃)₂, 12.18 Å for TbH(O₃PC₂H₅)₂, 14.84 Å for TbH(O₃PC₃H₇)₂ and 15.20 Å for TbH(O₃PC₆H₅)₂. The Tb³⁺ luminescence data revealed highly green emissive materials when they were excited at 368 nm, where the characteristic ⁵D₄ → ⁷F _J (J=6, 5, 4 and 3) transitions of Tb³⁺ were observed at 488, 543, 585 and 619 nm, respectively. The lifetime of the Tb^{3+ 5}D₄ → ⁷F₅ transition (λ_exc=368 nm and λ_em=543 nm) for the Tb³⁺ organophosphonates was evaluated from the decay curves, which values were of 2.88, 2.22, 2.14 and 2.59 ms, respectively for TbH(O₃PCH₃)₂, TbH(O₃PC₂H₅)₂, TbH(O₃PC₃H₇)₂ and TbH(O₃PC₆H₅)₂. TG analysis revealed that these materials are thermally highly stable, with no water molecule in their composition, which makes them potential luminophores.     

The geometry of organophosphonates: Fourier-transform microwave spectroscopy and ab initio study of diethyl methylphosphonate, diethyl ethylphosphonate, and diisopropyl methylphosphonate

The rotational spectra of diethyl methylphosphonate (DEMP), diethyl ethylphosphonate (DEEP), and diisopropyl methylphosphonate (DIMP) in supersonic expansions have been acquired using Fourier-transform microwave spectroscopy. Spectroscopic constants have been determined for five distinct conformers of the three molecules. Experimental data have been compared to ab initio calculations performed for each species. For both DEMP and DEEP, the calculations indicate the presence of several low-energy conformers (i.e., ?∼400 cm⁻¹ above the ground state) may be present at room temperature (300 K) for both DEMP and DEEP. When entrained in a supersonic expansion, the rotational temperatures of the samples are much colder (∼2 K); nonetheless, spectra from three conformers of DEEP are still observed experimentally, whereas only one conformer of DEMP is observed. In contrast, only a single low-energy conformer of DIMP is predicted by theory, and is present in the molecular beam. The relative abundance of low-energy conformers of DEMP and DEEP is attributed to the flexibility of the ethoxy groups within each molecule. The presence of multiple DEEP conformers in the supersonic beam indicates a more complex potential energy surface for this molecule that is directly related to conformational shifts of the PCH₂CH₃ group. Conversely, the absence of low-energy conformers of DIMP is attributed to steric hindrance between isopropoxy groups in the molecule. The internal rotation barrier for the PCH₃ group in DEMP and DIMP is compared to that found in DMMP and several phosphonate-based chemical weapon agents.     

Liquid–liquid–solid microextraction and detection of nerve agent simulants by on-membrane Fourier transform infrared spectroscopy

A coupling of novel liquid–liquid–solid microextraction (LLSME) technique based on porous hydrophobic membrane and Fourier-transform infrared spectroscopy has been presented for the detection, identification and quantification of markers and simulants of nerve agents. Two isomers O,O′-dihexyl methylphosphonate (DHMP) and O,O′-dipentyl isopropylphosphonate (DPIPP) were chosen as model analytes for the study. In the present technique, organic phase was immobilised within the pores of membrane after fixing it in an assembly, which was then immersed into aqueous sample of target analytes for extraction. The analytes were directly determined on the surface of membrane by FTIR spectroscopy without elution. On comparison with solid phase microextraction (SPME), LLSME was found to be much more efficient. The method was optimised and quantitative analyses were performed using calibration curves obtained via Beer's law and employing processing of spectra obtained, via a multivariate calibration technique partial least square (PLS). Relative standard deviations (RSDs) for intraday repeatability and interday reproducibility were found to be in the range of 0.20–0.50% and 0.20–0.60%, respectively. Limit of detection (LOD) was achieved up to 15 ng mL⁻¹. Applicability of the method was tested with an unknown real sample obtained in an international official proficiency test (OPT).