Davies, Stephen Robert (1989) Synthesis and characterisation of charge transfer complexes of new electron acceptors. Doctoral thesis, Durham University.
New electron acceptors, possessing various skeletal frameworks have been prepared and characterised. Complexation with a range of metal and organic cations reveal the suitability of the electron acceptors in the field of conducting charge-transfer complexes. Unsuccessful attempts to synthesise sterically demanding TCNQ derivatives, directly from the corresponding p-benzoquinone in the presence of titanium tetrachloride, provided a convenient route to a range of mono (dicyanomethylated)alkyl-p-benzoquinones, which were converted into N,7,7-tricyanoquinomethaneimine derivatives. Semi conducting charge-transfer salts of these new acceptors are described. Reduction of 2-dicyanomethylene-1,3-indandione (DCID) with cationic iodides, initiated a fascinating rearrangement to afford crystalline salts of the isomeric 2,3-dicyano-1,4-naphthoquinone (DCNQ), as confirmed by X-ray analysis.1,3-Metadinitrobenzene and 1,3,5-trinitrobenzene both form neutral, insulating, diamagnetic complexes with tetrathiafulvalene. The crystal structure of each complex is characterised by mixed stacks of alternate donor and acceptor molecules. The study of tetrachloro-DCID and l,3-bis(dicyanomethylene)indane further establishes that a wide range of electron acceptors belong in the development of organic metals.
|Item Type:||Thesis (Doctoral)|
|Award:||Doctor of Philosophy|
|Copyright:||Copyright of this thesis is held by the author|
|Deposited On:||08 Feb 2013 13:39|