The preparation of organosulfur derived electron transfer salts

BROOKS, A.C., 2009. The preparation of organosulfur derived electron transfer salts. PhD, Nottingham Trent University.

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Abstract

The concept of this thesis is to effect greater control over the crystalline state of radical cation salts in order to enhance electron transport, and to allow for the incorporation of additional functionality such as optical activity or magnetism. The salts formed are based on the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) framework, and are produced using the technique of electrocrystallisation. In attempts to control the crystal packing arrangements observed, a number of approaches have been explored including the incorporation of chirality, hydrogen bonding interactions and coordinate bonding interactions. These properties have been installed on the electron donor molecule and/ or the charge stabilising anion component. This thesis presents a novel radical cation salt that has been prepared from ET and the sulfamate anion, and which exhibits ordered channels of hydrogen bonded anions and water molecules extending in one crystallographic dimension. This research has also discovered an unusual chiral crystallographic packing observed in a novel semiconducting radical cation salt formed from ET and the bromide anion. Also presented are the synthesis of a family of metal-binding electron donors and the first radical cation salts formed from these, including a perrhenate salt which is both N-protonated and oxidised, giving an overall charge of +2 on the electron donor molecule. A group of novel aldehyde-functionalised donors are discussed, one of which could lead to a Little-type superconductor, and the syntheses towards a bis(donor) molecule containing a spiro centre, and separately a porphyrin appended electron donor are presented.

Item Type: Thesis
Creators: Brooks, A.C.
Date: 2009
Rights: This work is the intellectual property of the author, and may also be owned by the research sponsor(s) and/ or Nottingham Trent University. You may copy up to 5 % of this work for private study, or personal, non-commercial research. Any re-use of the information contained within this document should be fully referenced, quoting the author, title, university, degree level and pagination. Queries or requests for any other use, or if a more substantial copy is required, should be directed in the first instance to the author.
Divisions: Schools > School of Science and Technology
Depositing User: EPrints Services
Date Added: 09 Oct 2015 09:35
Last Modified: 09 Oct 2015 09:35
URI: http://irep.ntu.ac.uk/id/eprint/284

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