Electron nuclear double resonance measurements

As most of the nitroxyl spin-labelled synthetic derivatives of conjugated polyenes are light yellow crystals, the bond lengths were determined by X-ray crystallography38. The spectroscopic method used to measure the conformation is electron nuclear double resonance (ENDOR). It is beyond the scope of the present review to explain the method38 but the authors of the pertinent paper conclude that ENDOR is an accurate non-crystallographic method to determine polyene structures in solution. 

Electron-nuclear double resonance (ENDOR) spectroscopy A magnetic resonance spectroscopic technique for the determination of hyperfine interactions between electrons and nuclear spins. There are two principal techniques. In continuous-wave ENDOR the intensity of an electron paramagnetic resonance signal, partially saturated with microwave power, is measured as radio frequency is applied. In pulsed ENDOR the radio frequency is applied as pulses and the EPR signal is detected as a spin-echo. In each case an enhancement of the EPR signal is observed when the radiofrequency is in resonance with the coupled nuclei. 

The ENDOR technique refers to electron-nuclear double resonance. This consists of the effect on a partially saturated ESR line of simultaneously irradiating the sample with a radiofrequency to induce nuclear resonance transitions of hyperfine coupled nuclei. It may enable one to obtain information about signs of coupling constants. ELDOR is the technique corresponding to electron-electron double resonance. Such techniques, coupled with TRIPLE resonance, have been utilized and well described in a discussion of pyridine and 4,4-bipyridyl radical anion ESR spectra measured in sodium/liquid ammonia (80JMR<41)17). 

Electron spin resonance (ESR) measures the absorption spectra associated with the energy states produced from the ground state by interaction with the magnetic field. This review deals with the theory of these states, their description by a spin Hamiltonian and the transitions between these states induced by electromagnetic radiation. The dynamics of these transitions (spin-lattice relaxation times, etc.) are not considered. Also omitted are discussions of other methods of measuring spin Hamiltonian parameters such as nuclear magnetic resonance (NMR) and electron nuclear double resonance (ENDOR), although results obtained by these methods are included in Sec. VI. 

EPR but provides greatly enhanced resolution. Double resonance techniques (e.g. electron nuclear double resonance (ENDOR) and Overhauser shift measurements) combine the sensitivity of EPR with the resolution of NMR. Many such measurements on thin films are performed by combining optical detection with ENDOR, greatly enhancing the resolution of ODMR and taking advantage of its superior sensitivity. 

Electron-Nuclear Double Resonance (ENDOR) Spectroscopy. This observes a spin resonance transition after a nuclear resonance transition has been saturated by a radio-frequency pulse (Fig. 11.65) so as to invert the relative populations of the y.ey. > and y,./) .y> spin states this forces the populations of the aeaN> and fSey > states to be different and thus offers the opportunity to measure hyperfine splittings much more carefully, with better resolution than in standard EPR. 

MoOL2(Tp)] (L = OPh, SPh, or Cl) and related nitrosyl complexes, as also the dinuclear B-B linked complex reported in Fig. 2.26, have been investigated by electron magnetic resonance techniques, electron nuclear double resonance, and hyperfme sublevel correlation spectroscopy 11B hyperfme and quadrupolar couplings have been measured.120... 

There are also pulse EPR methods that probe the chemical or rather magnetic environment. These are pulse electron nuclear double resonance (ENDOR) and hyperfine sublevel correlation (HYSCORE) spectroscopy, which allow measuring hyperfine couplings from the unpaired electron spin to surrounding magnetically active nuclei ([20] in Fig. 3 this is a P nucleus). As these experiments are performed in frozen solution (e.g., in all examples of this chapter) or in solids, from the anisotropy and orientation dependence of the hyperfine coupling one can obtain valuable information on the structure up to 1 nm. 

Several experiments have been carried out to confirm the physical properties of solitons in mns-polyacetylene [27]. Lately, this excitation has also been studied in another degenerate ground state conjugate polymer, poly(l,6-heptadiene) [28]. The onedimensional spin diffusion and associated spin dynamics are verified from electron magnetic resonance spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and electron nuclear double resonance (ENDOR) measurements [13]. The density of neutral solitons has been estimated by Motsovoy and co-workers [29]. For more details on the physical properties of solitons, the reader is referred to a review article by Heeger and co-workers [13]. However, more theoretical and experimental work is... 

Hyperfine splitting due to interaction with ligand nuclei with 7 > 0 reflects the extent of spin delocalization onto neighboring atoms and can be used to characterize the types and numbers of such nuclei. In cases where these couplings are too small to be resolved in the EPR spectra, electron nuclear double resonance (ENDOR) or electron spin echo envelope modulation (ESEEM) can be used to measure the couplings as discussed in Chapter 2.3. Modern calculational tools are approaching the capabilities required to calculate g and A values from electronic wave functions. However, much of the spectroscopy that has been performed to date has used empirical correlations to interpret g and A values. 

For a sample to be EPR/ESR active, it must have one or more unpaired electrons. Stable free radicals, paramagnetic metal ions, and irradiated materials are some examples of such materials. The amount of sample required depends on the type of spectrometer (what band is used) and on the type of experiment—CW, pulsed, and double-resonance experiments like electron nuclear double resonance (ENDOR) (discussed in the following)—but in general, liquid and solid samples can be measured. Volumes of sample required range from 20 pL to 1 mL at concentrations of 10 nM to 20 mM for most experiments. 

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