Date of Award

2016

Publication Type

Doctoral Thesis

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

Keywords

CONDUCTIVITY, CRYSTAL ENGINEERING, LUMINESCENCE, MAGNETISM, NEUTRAL RADICALS, OLEDs

Supervisor

RAWSON, JEREMY

Rights

info:eu-repo/semantics/openAccess

Abstract

Chapter 1 provides an overview of the area of 1,2,3,5-dithiadiazolyl (DTDA) radical chemistry which is central to this thesis, including a review of the crystal engineering principles and the physical properties of DTDA radicals, focusing on structure-property relationships. The magnetic properties of the -polymorph of p-NCC6F4CNSSN have been almost exhaustively studied since 1993 when it was found to exhibit the highest magnetic ordering temperature (TN = 36 K) for an organic magnet. Conversely the structure and physical properties of the -polymorph have barely been explored. The conditions for the selective preparation of  and polymorphs of this radical are investigated in Chapter 2. The relative polymorph stability is probed through detailed DSC and PXRD studies and the magnetic properties of the -polymorph fully examined through dc and ac susceptibility measurements coupled with heat capacity studies. In Chapters 3 and 4, systematic structural studies on the variation of substituent groups are undertaken, comprising a series of alkoxy-functionalised perfluorophenyl DTDA radicals, p-ROC6F4CNSSN (R = Me, Et, Pr, Bu) and a comparison of the substitution pattern of the tolyl group on PhDTDA derivatives, MeC6H4C6H4CNSSN and their polymorphs. These studies use a combination of single crystal and VT-PXRD, SQUID magnetometry and VT EPR spectroscopy combined with DSC measurements and computational studies to probe relative polymorph stabilities and magnetic properties. A new generation of DTDA radicals where the R substituent is “non-innocent” are described in Chapters 5 and 6. In Chapter 5 the synthesis and characterisation of a series of DTDA-functionalised polyaromatic hydrocarbons (PAH) are described and their polymorphism examined as well as their solution and solid state optical properties. These reveal fluorescence quantum efficiencies up to 50%. Radical stability can be enhanced through incorporation into polymer matrices (PMMA and PS) which retard hydrolysis and prototype OLEDs based on a fluorescent DTDA exhibiting a luminance of almost 2000 Cd/m2 is described. Chapter 6 describes two stilbene-based DTDA diradicals in which the potential for thermal and photochemical cis/trans isomerisation, ring closure or [2+2] cycloaddition was explored. Solution photochemistry reactions, monitored by 1H NMR, UV/vis and fluorescence studies and EPR spectroscopy) revealed a trans/cis isomerisation, followed by ring-closure to afford a dihydrophenanthrene intermediate which undergoes H-atom migration with quenching of radical paramagnetism. Subsequent thermal treatment affords a phenanthrene-based diradical species with an increase in sample paramagnetism. Chapter 7 provides a brief overview of the results obtained in this thesis, the insight that these results provide within this research area and the potential for future exploitation.

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