Electron spin resonance , redox properties

Niobium- and tantalum-containing mesoporous molecular sieves MCM-41 have been studied by X-ray powder diffraction, 29Si MAS NMR, electron spin resonance, nitrogen adsorption and UV-Vis spectroscopy and compared with niobium- and tantalum-containing silicalite-1. The results of the physical characterization indicate that it is possible to prepare niobium- and tantalum-containing MCM-41 and silicalite-1, where isolated Nb(V) or Ta(V) species are connected to framework defect sites via formation of Nb-O-Si and Ta-O-Si bonds. The results of this study allow the preparation of microporous and mesoporous molecular sieves with remarkable redox properties (as revealed by ESR), making them potential catalysts for oxidation reactions. 

Huttermann J, Ward JF, Myers LS Jr (1971) Electron spin resonance studies of free radicals in irradiated single crystals of 5-methylcytosine. Int J Radiat PhysChem 3 117-129 Huttermann J, Ohlmann J, Schaefer A, Gatzweiler W (1991) The polymorphism of a cytosine anion studied by electron paramagnetic resonance spectroscopy. Int J Radiat Biol 59 1297-1311 Hwang CT, Stumpf CL, Yu Y-Q, Kentamaa HI (1999) Intrinsic acidity and redox properties of the adenine radical cation. Int J Mass Spectrom 182/183 253-259 Ide H, Otsuki N, Nishimoto S, Kagiya T (1985) Photoreduction of thymine glycol sensitized by aromatic amines in aqueous solution. J Chem Soc Perkin Trans 2 1387-1392 Idris Ali KM, Scholes G (1980) Analysis of radiolysis products of aqueous uracil + N20 solutions. J Chem Soc Faraday Trans 176 449-456... 

Copper and zinc containing mesoporous molecular sieves AIMCM-41 have been studied by MAS NMR, electron spin resonance, nitrogen and carbon monoxide adsorption and temperature programmed reduction. AlMCM-41 materials with ns,/nAi = 15, 30 and x have been synthesized in the presence of copper and zinc Carbon monoxide adsorption shows the presence of Cu ions after mild activation, but Zn ions have not been detected indicating that only a ZnO phase is formed Temperature programmed reduction reveals the presence of CuO clusters of various size depending on the on the ns./n ij ratio and the zinc concentration The results of this study allow the preparation of mesoporous molecular sieves with remarkable redox properties, which are potential model catalyst for methanol synthesis... 

The side chain can also affect electronic events of the tricyclic ring system. Electron spin resonance experiments allowed Fenner S to suggest that the influence of the side chain of phenothiazine on the formation of free radicals showed a correlation between the redox activity of the phenothiazine nucleus and dynamic aspects of stereochemistry. For example, there was a difference in the formation of cationic free radicals between promazine and alimemazine. The latter has a branched side chain, and forms cationic free radicals only under irradiation. It differs from promazine in pharmacodynamic properties, reported s to result in considerably shifted ion exchange equilibria. A kinetic study of the oxidation of dopamine by dialkylaminoalkyl phenothiazine cationic free radicals showed that a strong correlation existed between side-chain structures and oxidation rates phenothiazine free radicals with two carbon side chains had faster rates than those with three carbon side diains, albeit both were very rapid at physiological pH. 

The purpose of this monograph is to present some recent results involving the redox chemistry of some metal ion complexes, some of which contain very traditional and well established ligands, such as bipyridine (bipy), while others involve more esoteric ones, such as the cryptands. However, the main theme is not necessarily the electrochemistry of these complexes, nor their electron spin resonance (ESR) spectra, but rather the properties of the resulting redox products, whether in solution or in the solid state. Some of these redox products have been successfully crystallized, and some of their solid state properties have been measured, including X-ray diffraction and conductivities. These will be briefly presented. In addition, some of the properties of these reduced complexes in solution will also be presented and discussed. 

Part of the detailed characterizaion of these reduced ciyptates requires knowledge of their properties in solution. Most importantly, the number of redox electrons that can be added without appreciable decomposition is of interest. Also of interest is the question of whether the extra electrons added to the cryptates are localized in specific bipy structures, as was just described for the crystalline state, or whether they are able to "hop" between the bipy s. These specific questions are conveniently probed with a combination of electrochemical and electron spin resonance (ESR) techniques. 

Photosystem II (PSII) contains a remarkably stable tyrosine radical D", located at tyr-160 in the D2 polypeptide, which exhibits a well-known electron paramagnetic resonance (EPR) spectrum, EPR Signal Ilg (1). The function of D" " in the mechanism of photosynthetic H2O oxidation remains unclear despite evidence that it can oxidize the Mn complex, the H20-oxidation catalyst in PSII, from the Sq state to the normally daik-stable Si state (2). Several studies indicate that die oxidation state of the Mn complex influences the electron spin-lattice relaxation rate of D" (3-5), perhaps via a weak dipolar coupling, as suggested by Evelo et al. (5). Hence, the relaxation properties of D may provide a probe for the topology of redox-active sites in the 02-evolving center (OEC) and of the magnetic properties of the Mn complex. 

The role of the dopant potential on the stability and magnetic and optical properties of polarons and bipolarons in conducting polymers is shown with the aid of calculations of singlet and triplet states of a bipolaron [167] and by spectroelectrochemical and conductivity measurements [168-170]. The X-band optically detected magnetic resonance of PHT and PDDT shows that the distant intrachain polaron recombination is temperature-independent and identical in films and solutions. However, the triplet polaronic excitation decay is observable in films, but not in solutions [171], Electrochemical in situ conductivity and EPR measurements of PT films were performed in several solutions [172]. The results indicate that polarons merely seem to initiate the electrical conductivity. The electronic delocalization of polarons is restricted to a relatively short chain length at low potentials. As the polaron concentration increases (spin density maximum), bipolarons are generated immediately (probably too fast for the detection of polarons by EPR). Thus the bipolarons prevail in the fully conducting polymer films and as a consequence should be mainly responsible of the intrinsic conductivity [172]. Asymmetrically disub-stituted PBT display well-defined redox processes which are correlated to the consecutive formation of radical cations, dimerized radical cations, and dications [173]. 

---