Chemically induced magnetic spin signals

Time-resolved laser flash ESR spectroscopy generates radicals with nonequilibrium spin populations and causes spectra with unusual signal directions and intensities. The signals may show absorption, emission, or both and be enhanced as much as 100-fold. Deviations from Boltzmann intensities, first noted in 1963, are known as chemically induced dynamic electron polarization (CIDEP). Because the splitting pattern of the intermediate remains unaffected, the CIDEP enhancement facilitates the detection of short-lived radicals. A related technique, fluorescence detected magnetic resonance (FDMR) offers improved time resolution and its sensitivity exceeds that of ESR. The FDMR experiment probes short-lived radical ion pairs, which form reaction products in electronically excited states that decay radiatively. ... 

Chemically induced dynamic nuclear polarization (CIDNP) is a nuclear magnetic resonance method based on the observation of transient signals, typically substantially enhanced, in either absorption of emission. These effects are induced as a result of magnetic interactions in radical or radical ion pairs on the nanosecond time scale. This method requires acquisition of an NMR spectrum during (or within a few seconds of) the generation of the radical ion pairs. The CIDNP technique is applied in solution, typically at room temperature, and lends itself to modest time resolution. The first CIDNP effects were reported in 1967, and their potential as a mechanistic tool for radical pair reactions was soon recognized [117, 118]. Nuclear spin polarization effects were discovered in reactions of neutral radicals and experiments in the author s laboratory established that similar eflects could also be induced in radical ions [119-121]. 

CIDNP (chemically induced dynamic nuclear polarization) Non-Boltzmann nuclear spin state distribution produced in thermal or photochemical reactions, usually from colligation and diffusion, or disproportionation of radical pairs, and detected by nuclear magnetic resonance spectroscopy by enhanced absorption or emission signals. 

When a free radical is produced in a chemical reaction, the orientation of the electron spins with respect to the external magnetic field is random, so that in effect the electron spin states of the newly formed radicals are saturated. Thus if the newly formed radical is sufficiently short-lived, so that any nuclear polarization induced in the radical has not had time to decay before it becomes a diamagnetic molecule, when the n.m.r. signal is observable, an enhanced nuclear signal may be produced. Furthermore the relaxation of the electrons in the newly formed radicals may also induce nuclear spin polarization in other molecules in the solution. 

Another technique for the study of reactions that is highly specific for radical processes is known as CIDNP, an abbreviation for chemically induced dynamic nuclear polarization." The instrumentation required for such studies is a normal NMR spectrometer. CIDNP is observed as a strong perturbation of the intensity of NMR signals in products formed in certain types of free radical reactions. CIDNP is observed when the normal population of nuclear spin states dictated by the Boltzmann distribution is disturbed by the presence of an unpaired electron. The intense magnetic moment associated with an electron causes a polarization of nuclear spin states, which is manifested by enhanced absorption or emission, or both, in the NMR spectrum of the diamagnetic product of a free radical reaction. The technique is less general than EPR spectroscopy because not all free radicals can be expected to exhibit the phenomenon. 

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