The synthesis of oligothiophene functionalized dimethyldihydropyrenes and their electrical and photochromic properties

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dc.contributor.author Robinson, Stephen Garfield
dc.date.accessioned 2008-04-09T18:24:49Z
dc.date.available 2008-04-09T18:24:49Z
dc.date.copyright 2008 en_US
dc.date.issued 2008-04-09T18:24:49Z
dc.identifier.uri http://hdl.handle.net/1828/336
dc.description.abstract The synthesis of benzo[e]dimethyldihydropyrene (BDHP) photoswitches with ter-27, quarter-36, and quinque-28 thiophene oligomers attached on the same side of the switch was achieved using Stille coupling reactions. BDHP photoswitches with bi-75, ter-76 and quinque-77 thiophene oligomers attached directly to the switch on one side, and via a carbonyl spacer on the opposite side of the switch were also synthesized. Dimethyldihydropyrene (DHP) photoswitches with a naphthoyl functional group in the 2 position were synthesized using a Friedel Crafts reaction, and ter-96, quinque-97 and septi-98 thiophene oligomers were attached on opposite sides of the switch using Stille coupling reactions. All compounds were characterized by NMR, IR UV-vis spectroscopy and mass spectrometry. The relative rates of the photo-opening reactions under excess light conditions and the UV closing reactions versus BDHP were measured. Improvements in the photo-opening properties of the oligothiophene functionalized switches compared to BDHP were observed. The most dramatic photo-opening improvement was found for the quinquethienyl substituted DHP switch 97 which photo-opened when irradiated with visible light over 100 times faster than BDHP. UV closing rates were virtually the same as that of BDHP. However the addition of oligothiophenes led to an increase in the thermal closing reaction rates. Compounds with the naphthoyl functional group in the 2 position of DHP were found to have dramatically increased thermal closing rates. The electrochemical properties of oligothiophene functionalized BDHP and naphthoyl functionalized DHP switches in the closed form were studied by cyclic voltammetry and spectroelectrochemistry. During the oxidation cycle, a closing reaction from the cyclophanediene (CPD) form to the DHP form of the switches occurred which prevented the study of the electrochemical properties of the switches in the open form. Conductivity testing was performed on the quinquethienyl substituted DHP switch 97 using a gold interdigitated micro electrode array. The conductivity of undoped 97 was greater in the closed DHP isomer than in the open CPD isomer. Irradiation with red or blue light allowed for repetitive switching between the more highly conducting closed form and the less conducting open form. When electrochemically doped, 97 showed improved conductivity over the undoped form but only the conductivity of the closed doped form could be measured due to electrochemically induced closing. en_US
dc.language English eng
dc.language.iso en en_US
dc.rights Available to the World Wide Web en_US
dc.subject photochromism en_US
dc.subject dimethyldihydropyrene en_US
dc.subject benzodimethyldihydropyrene en_US
dc.subject cyclophanediene en_US
dc.subject oligothiophene en_US
dc.subject poly(thiophene) en_US
dc.subject photochromism en_US
dc.subject photochromic materials en_US
dc.subject conjugation en_US
dc.subject conductivity en_US
dc.subject aromaticity en_US
dc.subject ring current en_US
dc.subject spectroelectrochemistry en_US
dc.subject interdigitated micro electrode en_US
dc.subject Stille coupling en_US
dc.subject Weinreb amide en_US
dc.subject.lcsh UVic Subject Index::Sciences and Engineering::Chemistry en_US
dc.title The synthesis of oligothiophene functionalized dimethyldihydropyrenes and their electrical and photochromic properties en_US
dc.type Thesis en_US
dc.contributor.supervisor Mitchell, Reginald H.
dc.degree.department Dept. of Chemistry en_US
dc.degree.level Doctor of Philosophy Ph.D. en_US

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