Effect of Shift Reagents on Infrared Spectra

Abstract

Introduction

We have shown previously¹ that when Eu(fod)₃?d₂₇ shift reagent is added to the erythro and threo esters of 2,3-diphenyl-3-hydroxypropanoic acid, the vicinal coupling constants, J₂₃, vary in a manner which indicates bidentate coordination.     

Lanthanide Shift Reagents. Paper 21. Interaction of Arenes with Silver/Lanthanide Shift Reagent and Comparison with Chromium Tricarbonyl Complexes

Lanthanide shift reagents can bring about dramatic simplifications of highly complex NMR spectra^1,2. The applicability of the commonest of these (the thd and fod chelates of Eu, Pr and Yb) has been restricted to those molecules possessing a suitable N, O or S donor atom, although they may turn up in unusual guises, e.g. in quaternary ammonium compounds³.     

Binuclear NMR Shift Reagents. An Apparent Anomalous Effect with Vinclozolin

The 60 MHz ¹H NMR spectra of racemic vinclozolin, 1, have been studied at 28° in CDC1₃ solution with the chiral reagent tris[3-(heptafluoropropylhydroxymethylene)-d-camphorato]europium(III), 2, by incremental additions of (6,6,7,7,8,8,8-heptafluoro-2,2-di-methyl-3,5-octanedionato)silver(I), 3. Although the solution of 1 with 2 displayed substantial downfield lanthanide-induced shifts, Δδ, and enantiomeric shift differences, ΔΔδ, for selected nuclei, relative to the spectrum of unshifted 1, additions of 3 to the solution of 1 and 2 were unexpectedly found to dramatically reduce the magnitudes of both Δδ and ΔΔδ.     

Optical properties of Eu(fod)3-doped polymers using supercritical carbon dioxide

X-ray diffraction pattern of solvated Eu(fod)₃(H₂O)_1,5(i-PrOH)_0,5 form of Eu(fod)₃ complex (fod=6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate) is presented. The photoluminescence (PL) spectra of Eu³⁺ ions in polycrystalline powder Eu(fod)₃ and also in Eu(fod)₃-doped polymethylmethacrylate (PMMA), polypropylene (PP) and polydimethylsiloxane (PDMS) were investigated. It is revealed that the matrix influences the temperature quenching of PL intensity in the range 20-100 °C. A polycrystalline powder Eu(fod)₃ and Eu(fod)₃-doped PP are the most effective materials for PL quenching. It is shown that water molecules in the first coordinating sphere of Eu³⁺ ions increase PL intensity temperature quenching.     

Lanthanide Shift Reagents: Acetylacetone Complex of Yb(III) Ion

It has recently been shown that the 2,2,6,6-tetra-methylheptane-3,5-dione (tmhd) complexes of a number of lanthanide ions possess the useful property of inducing large chemical shifts in the proton NMR spectra of certain compounds containing OH or other nucleophilic groups^1–8. The resulting spectra are frequently more readily assignable and analysable. Although europium and praseodymium appear to be the most suitable ions for such studies, the shifting effect is also observed with other lanthanide ions.^5,6     

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Meparfynol, 3-Methyl-L-Pentyn-3-Ol. Apparent Anomalous Results with a Binuclear Shift Reagent

The 60 MHz ¹H NMR spectra of racemic meparfynol, 1, have been studied in CDCl₃ solution at 28° with the achiral shift reagentt tris(6,6,7,7,8,8,8-hepta-fluoro-2,2-dimethyl-3,5-octanedionato) europium (III), 2, and the chiral reagent, tris[3-(heptafluoropropyl-hydroxymethylene)-d-camphorat01 europium(III), 3. With 3, observable enantiomeric shift differences for the 3-methyl should make possible direct optical purity determinations. Additions of increments of (6,6,7,7,8,8,8-heptafluoro-2,2-dimenthyl-3,5-octane-dionato)silver(I) 4, to a CDCl₃ solution of 1 and 3 resulted in changes in Δδ magnitudes and in some line intensities that are discussed in terms of interactions with the ethynyl and hydroxyl groups.     

Thermal quenching of photoluminescence of Eu3+ ions in an Eu(fod)3 complex

We have studied the photoluminescence (PL) spectra of Eu³⁺ ions in the complex Eu(fod)₃ (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione) and also in polymers doped with Eu(fod)₃ with the help of supercritical carbon dioxide. We have established that in the temperature range 20°C–100°C, we observe thermal quenching of the photoluminescence of Eu³⁺ ions, and this quenching is most efficient in polycrystalline Eu(fod)₃ powder and Eu(fod)₃-doped polypropylene. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 315–319, May–June, 2006.     

Laser fabrication of periodic microstructures from silver nanoparticles in polymer films

The fabrication of photoand thermostable periodic structures from silver nanoparticles in polymer plates (cross-linked oligourethanemethacrylate impregnated with silver precursors Ag(hfac) and Ag(fod) dissolved in the supercritical carbon dioxide) is studied. The process is based on the local (depending on the irradiated spot size) photochemical decomposition of the silver precursors in the polymer matrix that initiates the atomic aggregation and creation of silver nanoparticles with the plasmon resonance in absorption in the spectral range 420–430 nm. The third-harmonic radiation of a Nd:YAG laser (355 nm) and the Kr⁺-laser (521 nm) radiation are employed for the recording of periodic structures with submillimeter and micron resolutions. The photosensitivity of the polymer matrices impregnated with the silver precursors to the UV and visible radiation is discussed.     

Lanthanide Shift Reagents XIV Equilibrium Binding Constants for Europium Shift Reagent with Alkyl and Aryl Esters

Methods have been developed for measuring the equilibrium binding constants (K) for lanthanide shift reagents with donor substrates. Although Infrared Spectroscopy proved useful¹ for determining the binding of substituted anilines to the tris-tetramethylheptanedionate of Ytterbium, it was found that NMR was more sensitive and applicable to a wider range of substrates than simple alcohols and amines^2,3. The NMR procedure of progressive     

NMR Studies of Drugs. Applications of Achiral and Chiral Wthanide Shift Reagents to Bupropion

Abstract

The ¹H NMR spectra of racemic samples of the antidepressant drug, bupropion, 1, have been studied in CDCl₃ solution at 60 and 200 MHz with the achiral lanthanide shift reagent (LSR), tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium (III), 2, and the chiral reagent, tris[3-(heptafluoropropylhydroxymethylene)-d-camphorato]europium(III), 3. Both LSR produced substantial lanthanide induced shifts consistent with ¹H assignments, but the bound complexes of 1 with 2 versus 3 may not be isostructural. With 3, substantial enantiomeric shift differences were observed for the t-butyl, CH ₃CH, NCH, and the aryl H-2 and H-6 signals, which should permit potential direct determination of enantiomeric excess.     

NMR Studies of Drugs. Applications of Lanthanide Shift Reagents to Afloqualone,an Axially Chiral Quinazolinone.

The skeletal muscle relaxant, aflogualone, 1, has been studied by ¹H NMR in CDC1₃ at 60 and 300 MHz in the presence of added chiral [Eu(HFC)₃] or achiral [Eu(FOD)₃] lanthanide shift reagents (LSR). With Eu(HFC)₃, significant enantiomeric shift differences, ΔΔδ, can be induced for most of the nuclei of 1, with near-baseline resolution obtainable for the H-5 signals of each enantiomer, indicating excellent analytical potential for direct determination of enantiomeric excess of samples of 1. Observation of ΔΔδ directly confirms hindered rotation about the bond between N (3) and the 2-methylphenyl group, i.e., the N (sp²) - C(sp²) bond, leading to axial chirality in 1 with slow rotation on the NMR timescale. Assignments are supported by 2D COSY spectra at 300 MHz. Relative lanthanide-induced shift magnitudes for the protons of 1 are compared.     

Lanthanide Shift Reagents. Paper 18. Equilibrium Binding Constants for Europium Shift Reagent with Nitrogen Heterocycles

Paper 16 in this series^{1, 2, 3} was concerned with the equilibrium binding constants (K) of the shift reagent Europium tris (2, 2, 6, 6-tetramethylheptane-3, 5-dionate), Eu(thd)₃, with primary, secondary and tertiary amines. One nitrogen heterocycle, pyridine, and two of its derivatives (see Table) were included. In the present paper we describe the binding constants for a further 9 nitrogen containing heterocycles and relate these to basicity and steric effects.     

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Lofexidine

The ¹H NMR spectra of the potent anti-hypertensive drug, lofexidine, 1, have been studied in CDCl₃ at 60 and 300 MHz. Both the achiral shift reagentr tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionatol-europium(III), 2 and the chiral reagents1 tris[3-(heptafluoropropylhydroxymethylenel-d-camphoratoleuropium(III), 3 and tris[3-(trifluoromethylhydroxymethylenel-d-camphoratoleuropium(III), 4, were employed. Substantial lanthanide induced shifts were observed with 2, 3 or 4, with the largest shifts seen for the methine at the chiral centerr followed by the signal of the NH. Enantiomeric shift differences for the CH₃ signal of 1 were seen with 3 OK 4, with 4 inducing larger values of potential analytical utility. Using a non-racemic sample of 1, the (-) enantiomer was shown to have a downfield sense of magnetic nonequivalence for the methyl resonance in the presence of added 4.     

Effect of the external medium on the spectral characteristics of polypropylene films doped with Eu(fod)<Subscript>3</Subscript> molecules

We have studied the effect of external factors (humidity, pressure, temperature) on the stability of the organometallic compound Eu(fod)3 (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione) impregnated into polypropylene (PP) using supercritical CO₂. We have established that under the influence of external conditions, there is a decrease in the integrated intensity of the absorption band for the Eu(fod)₃ molecule and the photoluminescence (PL) of Eu³⁺ ions as a function of the properties of the medium, and in the presence of water molecules the shape of the bands for these spectra changes. We propose a physical model explaining the behavior of the absorption and photoluminescence spectra when the polypropylene films are stored under different conditions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 42–47, January–February, 2007.     

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Mexiletine

The 60 MHz ¹H NMR spectra of mexiletine, 1-(2,6-dimethylphenoxy)-2-propanamine, 1, have been studied at 28° in CDCl₃ solution with the achiral reagent, tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium(III), 2, Eu(FOD)₃, and the chiral reagents tris[3-(trifluoromethylhydroxymethylene)-d-camphorato]europium(III), 3, Eu(FACAM)₃, and tris[3-(heptafluoropropylhydroxymethylene)-d-camphorato]europium(III), 4, Eu(HFC)₃. Substantial lanthanide-induced shifts were seen for the proton signals of 1 with each reagent. Appreciable enantiomeric shift differences were seen for both methyl signals and for each of the CH₂CH proton signals using 3 and 4 that should permit direct determinations of enantiomeric excess for samples of 1. A predominant conformation for 1 is suggested based on observed splittings of the CH₂ proton signals and their relative lanthanide-induced shifts.     

Hypersensitivity in the Luminescence and 4f?C4f Absorption Properties of Mono- and Dinuclear EuIII and ErIII Complexes Based on Fluorinated ??-Diketone and Diimine/ Bis-Diimine Ligands

The results of our investigation on the sensitized luminescence properties of three Eu(III) ??-diketonate complexes of the form [Eu₂(fod)₆(??-bpm)], [Eu(fod)₃(phen)] and [Eu(fod)₃(bpy)] and 4f?C4f absorption properties of their Er(III) analogues ( fod = anion of 6,6,7,7,8,8,8- heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2??-bipyrimidine, phen = 1,10-phenanthroline and bpy = 2,2??-bipyridyl) in a series of non-aqueous solvents are presented. The Eu(III) complexes are highly luminescent and their luminescence properties (intensity and band shape) are sensitive to the changes in the inner coordination sphere of the Eu(III) ion. The luminescence intensity of the mononuclear complexes in pyridine is drastically decreased. The coordination structure of the complexes in pyridine is transformed into a more symmetrical one which results into a slow radiative rate of the emission from the complexes. The ancillary ligands, phen and bpy are found better co-sensitizers as compared to the bpm to sensitize Eu(III)-luminescence. The 4f?C4f absorption properties (oscillator strength and band shape) of the Er(III) complexes demonstrate that ⁴G_11/2 ?? ⁴I_11/2 and ²H_11/2 ?? ⁴I_15/2 hypersensitive transitions of Er(III) are very sensitive in some coordinating solvents which reflects complex?Csolvent interaction in solution. The hypersensitive transitions of [Er(fod)₃(phen)] remain unaffected in any of the solvents and this complex retains its bulk composition in solution. The erbium complexes as well as the Er(fod)₃ chelate are invaded by DMSO. This solvent enters the inner coordination sphere by replacing heterocyclic ligand and the complexes acquire similar structure [Er(fod)₃(DMSO)₂] in this solvent. The results reveal that the luminescence and absorption properties of lanthanide complexes in solution can be controlled by tuning the coordination structure through ancillary ligands and donor solvents. This work shall prove useful in designing new biological applications with such probes.     

Lanthanide Shift Reagents XIII the Influence of Phenyl, 1-Adamantyl and Tert-Butyl Substituents on Equilibrium Constants

We have recently extended our Infrared studies of the binding of anilines with lanthanide shift reagents¹ to an NMR examination of hindered phenyl-carbinols² and a series of aldehydes and ketones related to benzaldehyde and acetophenone³.     

Photoluminescence, optical absorption and hypersensitivity in mono- and dinuclear lanthanide (Tb and Ho) β-diketonate complexes with diimines and bis-diimine bridging ligand

The photoluminescence properties of three Tb(III) complexes of the form [Tb₂(fod)₆(μ-bpm)], [Tb(fod)₃(phen)] and [Tb(fod)₃(bpy)] and optical absorption properties of their Ho(III) analogues (fod=anion of 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm=2,2′-bipyrimidine, phen=1,10-phenanthroline and bpy=2,2′-bipyridyl) in a series of solvents are presented. The luminescence of the complexes is sensitive to changes in environment (ligand/solvent) around Tb(III) and co-sensitization of the ancillary ligands. The enhancement of the luminescence intensity in coordinating solvents is attributed to the transformation of eight-coordination into less symmetric nine-coordination structure around Tb(III). Among phen and bpy, the phen is better co-sensitizer while bpm has been observed as poor co-sensitizer. The enhancement of the oscillator strength of ⁵G₆←⁵I₈ hypersensitive transition in the 4f-4f absorption in some coordinating solvents is attributed to decrease in the symmetry of the field around Ho(III) ion. The [Ho(fod)₃(phen)] is inert towards the solvents and retains its bulk structure and composition in solution. The transformation of the holmium complexes in DMSO into [Ho(fod)₃(DMSO)₂] species is found. The results reveal that the luminescence and 4f-4f absorption properties of lanthanide complexes in solution can be modulated by tuning the coordination structure through ancillary ligands and donor solvents.     

NMR Studies of Drugs. Applications of Achiral and Chiral Lanthanide Shift Reagents to a 5-Substituted-4-thiazolidinone

The 60 MHz ¹H NMR spectra of racemic 5-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-4-thiazolidinone, 1, have been studied in CDCl₃ solution at 28° with the achiral lanthanide shift reagent (LSR), tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium (III), 2, and the chiral LSRs, tris[3-(heptafluoropropylhydroxymethylene)- (+)-camphoratojeuropium(III), 3, and tris[3-(trifluoromethylhydroxymethylene-(+) -camphorato]europium (III), 4, Significant enantiomeric shift differences were observed in the presence of added 3, for the aryl protons of 1 that should permit direct determination of enantiomeric excess. Relative magnitudes of lanthanide-induced shift for the different nuclei of 1 with the three LSRs are compared and discussed in terms of preferred LSR binding sites. A favored conformation of 1 with respect to rotation about the C(5)-CH₂ bond is suggested.     

NMR Studies of Drugs. Sulindac Methyl Ester. Applications of Achiral and Chiral Lanthanide Shift Reagents

The potent nonsteroidal anti-inflammatory agent, sulindac, (Z) -5-fluoro-2-methyl-1-{[4-(methylsulfinyl) - phenyl]methylene} -1H-indene-3-acetic acid, has been examined by ¹H NMR as its methyl ester in CDCl₃ solution with the added achiral lanthanide shift reagent (LSR) tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium (III), Eu (FOD)₃, 2, for spectral simplification, and with the chiral LSRs, tris[3-(heptafluoropropylhydroxymethylene) - (+) - camphorato] europium (III), 3, and tris[3-(trifluoromethyl-hydroxymethylene) - (+) -camphorato] europium (III), 4, to induce enantiomeric shift differences (ΔΔδ) for several nuclei. Studies employed 60 and 300 MHz spectrometers. At the higher frequency, analytically useful ΔΔδ values were observed with added 3 for the aryl protons ortho to the methylsulfinyl group that should permit direct determinations of enantiomeric excess (% ee). By conversion of sulindac samples to the methyl ester, use of 3 would then formally constitute an ee determination of sulindac.