1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...
1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...
1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...
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temperature. 64 This w<strong>as</strong> a very important discovery <strong>as</strong> bistability is a key property in<br />
developing new devices for functions such <strong>as</strong> data storage, switching units <strong>and</strong> sensors<br />
for heat or light. 65<br />
Within a certain temperature regime, compounds which exhibit<br />
bistability can exist in at le<strong>as</strong>t two different polymorophic forms <strong>and</strong> the sample history is<br />
important in determining which of these will be dominant at a given temperature.<br />
Compound I-14a for example exists only <strong>as</strong> what is called the high-temperature ph<strong>as</strong>e<br />
when heated above 320 K <strong>and</strong> exhibits paramagnetic properties, where<strong>as</strong> if it is cooled to<br />
below 210 K it only exists <strong>as</strong> the low temperature ph<strong>as</strong>e which is diamagnetic. This<br />
compound will be revisited in section 1.3 when its copper coordination complex is<br />
examined.<br />
1.3.3 <strong>Dithiadiazolyl</strong> <strong>Radicals</strong> <strong>and</strong> Their Selenium Analogues<br />
1.3.3.1 1,2,3,5-Dithiadiaozlyl <strong>Radicals</strong> (1-16)<br />
The cl<strong>as</strong>s of compounds 1,3,2,4-DTDAs b<strong>as</strong>ed on the I-15 framework, can be<br />
isolated by a quantitative cycloaddition of SNS + with nitriles to give the corresponding<br />
heterocyclic, closed-shell cation. 66,67 One of the most interesting features that they exhibit<br />
is that they isomerise readily via a rearrangement to give the more thermodynamically<br />
stable 1,2,3,5-dithiadiazolyl radical (I-16). 68-70<br />
The SOMO for I-15 h<strong>as</strong> a much larger<br />
coefficient on the nitrogen atom between the two sulfur atoms than the nitrogen atom<br />
adjacent to the carbon. This is evident from EPR spectroscopy which gives only a three<br />
line pattern, indicative of coupling to only one nitrogen atom. 71 By contr<strong>as</strong>t, the SOMO<br />
for I-16 is nodal at the carbon atom which places a significantly larger amount of the<br />
21