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Matrix isolation method development

For full information on the development of matrix isolation methods and their application, the reader is referred to several monographs. " ... [Pg.6]

The matrix isolation method combined with ionizing radiation (i.e., y-rays, X-rays, etc.) at low temperature is versatile and has been extensively developed for ESR study of radical ions [3-13]. The procedure consists of dissolution of the solute molecule (atom) of interest in an appropriate solvent (matrix), freezing at low temperature (in general below 77 K), irradiation (or illumination), and ESR measurements before and after thermal treatment. The solvent molecules (atoms) are ionized by the irradiation to yield an electron (e ) and a positive hole (h ). The electron is transferred in general to a solute molecule with higher electron affinity than that of the solvent molecule to form a solute molecular radical anion (Fig. 5.2). On the other hand, the positive hole is transferred to a solute molecule with first ionization energy (potential) lower than that of the matrix molecule, resulting in the... [Pg.212]

During recent years, fascinating developments have occurred in the area of r 2-silene complexes, which opened up to totally new chemistry. Some of the highlights will be presented in this section. The first investigations of coordination compounds of silenes were carried out by means of matrix isolation techniques at very low temperatures. In particular, photochemical methods proved to be most effective... [Pg.37]

The results described in this review show that matrix stabilization of reactive organic intermediates at extremely low temperatures and their subsequent spectroscopic detection are convenient ways of structural investigation of these species. IR spectroscopy is the most useful technique for the identification of matrix-isolated molecules. Nevertheless, the complete study of the spectral properties and the structure of intermediates frozen in inert matrices is achieved when the IR spectroscopy is combined with UV and esr spectroscopic methods. At present theoretical calculations render considerable assistance for the explanation of the experimental spectra. Thus, along with the development of the experimental technique, matrix studies are becoming more and more complex. This fact allows one to expect further progress in the matrix spectroscopy of many more organic intermediates. [Pg.56]

The application of matrix isolation to organometallic chemistry has been extensively described elsewhere (4,5,6,7). Two methods have generally been employed. In the first, based on G.C. Pimentel s original development, the solid matrix environment is a frozen noble gas - usually Ar - at 10-20K and the unstable fragment is generated either by photolysis of a parent molecule already trapped in the matrix, or by cocondensation from the gas phase. In the... [Pg.114]

The identification of unknown chemical compounds isolated in inert gas matrices is nowadays facilitated by comparison of the measured IR spectra with those computed at reliable levels of ab initio or density functional theory (DFT). Furthermore, the observed reactivity of matrix isolated species can in some instances be explained with the help of computed reaction energies and barriers for intramolecular rearrangements. Hence, electronic structure methods developed into a useful tool for the matrix isolation community. In this chapter, we will give an overview of the various theoretical methods and their limitations when employed in carbene chemistry. For a more detailed qualitative description of the merits and drawbacks of commonly used electronic structure methods, especially for open-shell systems, the reader is referred to the introductory guide of Bally and Borden.29... [Pg.162]

To investigate radicals in high-temperature reactions, Lunsford developed a matrix isolation technique (MIESR, Section II.B) by which short-lived radical intermediates escaping from the catalyst surface into the gas phase are quenched in a matrix of solidified inert gas to enable their identification at low temperatures. Examples presented below illustrate the method. [Pg.292]

The theory of rotation effects on prolate luminescent molecules in solution and its experimental verification have been developed and compared. Generalized diffusion equations for the rotational motion of an asymmetric rigid motor have been used to given an expression for steady-state fluorescence depolarization. " The radiationless transition from the first excited singlet state of Eosin has been measured by optoacoustic relaxation, and the absolute fluorescence quantum yields of organic dyes in poly(vinyl alcohol) have also been measured by the photoacoustic method. The accuracy of the method has been discussed in the latter paper. Actinometry in flash photolysis experiments has been assisted by new measurements on the extinction coefficient of triplet benzophenone. Matrix-isolation fluorescence spectrometry has been used to detect polycyclic aromatic hydrocarbons from gas chromatography. ... [Pg.6]

Sample handling is a very important part of the method development for HPLC determination of phenolic acids in natural plants. Because of the great variability of phenolic acids (different polarity, acidity, number of hydroxyl groups, and aromatic rings), the various concentration levels of individual analytes, and the very complex natural matrix with many interfering components, the choice of the technique for their isolation and quantification differs from one described HPLC assay to the next. In some cases, only a one-step extraction and simple clean-up procedure are sufficient before the HPLC analysis, but the most often described HPLC assays include two or more steps of sample preparation, especially in the case of fruits and vegetable samples. It is obvious that each step contributes, on one hand, to the higher sensitivity and selectivity, but, on the other hand, it could increase the number of errors and decrease the recovery of the method. [Pg.1170]

An understanding of the mechanisms of solid-phase extraction (SPE) are crucial for effective methods development. The four mechanisms outlined in Chapter 2 are sufficient for the majority of SPE and are an effective set of tools for methods development. The molecule s structure and the sample matrix are the main features used to choose a mechanism of isolation and separation. This chapter will discuss a six-step approach to methods development, how to execute the SPE recovery experiment, troubleshooting and optimizing conditions for the SPE recovery experiment, and how to critically evaluate previously published methods. [Pg.51]

Also, the techniques of pulse radlolysls and matrix Isolation can frequently be used to characterize Ionic Intermediates. Indeed, recent developments have shown that y-lrradlatlon of Freon solid solids at 77 K provides a most useful method of generating solute radical cations for ESR studies (23), and we have applied this method to study the radical cations of several simple epoxides (24). [Pg.354]


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