Subject reverse electron correlation

The cyclic voltammetry characteristics of the nitroaniline-containing molecular scale devices were determined to help elucidate the transport mechanism. It was therefore necessary to synthesize thioether 73 that is more stable to hydrolysis and subsequent oxidation than the thioacetate-terminated system (Scheme 3.34). For the synthesis of thioether 73, intermediate 69 was deprotected and Pd/Cu-catalyzed coupled to 72 to form thioether terminated 73. This compound was subjected to cyclic voltammetry that confirmed that the compound was being reduced at -1.7 V and again reduced at -2.3 V (Ag/AgNOs reference electrode, 1.0 M n-tetrabutylammonium tetrafluoroborate in DMF at a scan rate of 100 mV/sec). Of course, there can be no correlation of absolute reduction potentials between the solution-phase and SAM experiments since the environments are grossly different. However, that 73 could undergo a reversible 2-electron reduction was useful in the development of a hypothesis of a mechanism of the transport effect. ... 

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