Chemically induced dynamic nuclear phenomenon

The first reports of the observation of transient emission and enhanced absorption signals in the H-n.m.r. spectra of solutions in which radical reactions were taking place appeared in 1967. The importance of the phenomenon, named Chemically Induced Dynamic Nuclear Spin Polarization (CIDNP), in radical chemistry was quickly recognized. Since that time, an explosive growth in the number of publications on the subject has occurred and CIDNP has been detected in H, C, N, and P as well as H-n.m.r. spectra. Nevertheless, the number of groups engaged in research in this area is comparatively small. This may be a consequence of the apparent complexity of the subject. It is the purpose of this review to describe in a quahtative way the origin of CIDNP and to survey the published applications of the phenomenon in... 

H. R. Ward, "Chemically Induced Dynamic Nuclear Polarization (CIDNP). I. The Phenomenon, Examples, and Applications, Accfs. Chem. Res. 5, 18 (1972). 

Chemically induced dynamic nuclear polarization is a spectroscopic technique that takes advantage of the coupling between electron and nuclear spins to detect products of radical recombinations by nuclear resonance. It is suited to investigation of the dynamics of radical processes, particularly the events just preceding radical recombinations. First observed in 1967 by Bargon and Fischer32 and independently by Ward and Lawler,33 the phenomenon consists of... 

One of the most important phenomenon, chemically induced dynamic nuclear polarization (CIDNP), deserves more detailed consideration, since it forms the basis of one of the most powerful modem methods for the investigation of the structure and reactivity of short-lived (from nano- to microseconds) paramagnetic precursors of the reaction products. CIDNP manifests itself in the form of unusual line intensities and/or phases of NMR signals observed when the radical reaction takes place directly in the probe of the spectrometer. These anomalous NMR signals—enhanced absorption or emission — are observed within the time of nuclear relaxation of the diamagnetic molecule (from several seconds to several minutes). Later on, the NMR spectrum re-acquires its equilibrium form. 

The photolyses of dlbenzyl ketones in aqueous micellar solution have been shown to greatly enhance both geminate radical pair recombination and the enrichment of in recovered ketone compared to homogeneous solution. These observations have been attributed to the combined effects of the reduced dimensionality imposed by mlcelllzatlon and hyperflne induced intersystem crossing In the geminate radical pairs. This latter effect is the basis of Chemically Induced Dynamic Nuclear Polarization (CIDNP), a phenomenon which is well known in homogeneous solution. 

The first discovery of chemically induced dynamic electron polarization (CIDEP) was made by Fessenden and Schuler in 1963 (58). These authors observed the abnormal spectra of the H atoms produced during the irradiation of liquid methane. The low-field line in the esr spectrum was inverted compared to the corresponding high-field line. The related chemically induced dynamic nuclear polarization effect (CIDNP) was reported independently four years later by Bargon et al. (22) and by Ward and Lawler (134). Because of the wider application of nmr in chemistry, the CIDNP effect immediately attracted considerable theoretical and experimental attention, and an elegant theory based on a radical-pair model (RPM) was advanced to explain the effect. The remarkable development of the radical-pair theory has obviously brought cross-fertilization to the then-lesser-known CIDEP phenomenon. 

The overall multiplicity of geminate radical pairs formed by bond fission is the same as that of the precursor excited state. Remarkably, the multiplicity of the precursor can often be established by NMR spectroscopy of the final products thanks to a phenomenon called chemically induced dynamic nuclear polarization (CIDNP, Special Topic 5.3). 

Attempts have been made to establish the intermediate formation of the radicals ArH and X by using the phenomenon of chemically induced dynamic nuclear polarization por example, the interaction of benzenediazoniiun tetrafluoroborate... 

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. 

Enhanced absorption and emission lines are detected in the NMR spectra of peroxides and azo compounds subjected to rapid decomposition.This phenomenon, referred to as chemically induced dynamic nuclear polarization (CIDNP), was first detected during the free-radical-initiated homopolymerization of CIDNP does not arise in reactions where radical transfer... 

The chemically induced dynamic nuclear polarization (CIDNP) phenomenon, (the occurrence of intense emission and enhanced absorption lines in high-resolution NMR spectra during chemical reactions) has been applied to the study of the photodegradation of poly(methyl isopropenyl ketone) [177]. 

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