Methodology for the synthesis of p-phenylenediamine derivatives for applications toward molecular devices

Selective substitution of chloride from cyclopentadienyl (p-dichlorobenzene)ruthenium by using secondary amines as nucleophiles has been successfully applied to synthesize a number of p-phenylenediamine derivatives as potential molecular rectifiers, and voltammetric or fluorescent chemosensors. This selectivity, in combination with further manipulation of the complexes, allows the preparation of unsymmetrically functionalized tetraalkyl- p-phenylenediamine (TAPD) units which are difficult to synthesize by traditional nucleophilic aromatic substitution (SNAr) conditions.; A series of TAPD and Donor-σ-Acceptor (D-σ-A) molecules, incorporating p-phenylenediamine as donor, having thioalkyl side chains that allow adsorption, e.g., onto a gold surface, has been synthesized.*; *Please refer to dissertation for diagrams.