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Content archived on 2022-12-23

Structure and reactivity of organic radical cations in ground and excited states in solids

Objective



Reactive organic radical cations occur as principal intermediates in a wide variety of oxidative processes, including radiation-chemical, photochemical, electrochemical, catalytic and other reactions. The present project aims at deeper understanding of internal and external factors controlling basic properties of organic radical cations in condensed media in ground and excited states, establishing correlations between the electronic structures of the radical cations and their observed reactivities, and studying the aspects of "transition-state selectivity" in radical cation mediated processes.

The following specific studies are planned: - examining basic spectroscopic properties of the radical cations and effect of ionization on chemical bonding using combined ESR and IR spectroscopic studies in solid rare gas matrices; - studying the matrix effects on structure and properties of the radical cations from energetic, structural and dynamic points of view; - investigating the properties of excited states and photochemistry of radical cations by ESR and UV/vis spectroscopy; - investigating molecular structure and thermal reactivity of organic radical cations as formed by one-electron oxidation in zeolite matrices to delineate the involvement of redox processes/radical cation reactions in zeolites, aspects of transition-state selectivity and relevance to heterogeneous catalysis; - obtaining detailed information about the electronic structure, dynamics and matrix-cation interactions in halocarbon and zeolite matrices using ENDOR, pulsed EPR, and pulsed ENDOR.

These studies will be based on novel experimental approaches and techniques developed by the participating groups: combination of low-temperature ESR and IR spectroscopy for studying radical cations in solid rare gas and halocarbon matrices; use of spin trapping techniques to characterize the products of radical cation reactions; application of zeolite matrices with variable structure and micropore size to probe the mechanism and selectivity of the reactions of radical cations; use of advanced magnetic resonance methods (ENDOR, pulsed EPR, and pulsed ENDOR) for studying the structure and dynamics of radical cations and matrix-cation interactions.

The participating groups are intersupplementary in approaches and techniques used. The joint research team appears to be a unique collective, which is able to carry out the investigations over the planned wide range. The results of studies will be presented in the form of scientific papers. It is planned to publish at least two papers after the first year of the project period and at least five papers totally. If possible the papers should be prepared jointly, with contributions from the different groups.

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Programme(s)

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Funding Scheme

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Coordinator

Linköping University
EU contribution
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Address

58183 Linköping
Sweden

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Total cost

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Participants (1)

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