Synthesis and characterization of oligomeric/polymeric assemblies as organic based molecular magnetic materials

The synthesis and characterization of three novel pi-conjugated polymers, bearing pendant semiquinone repeat units, are described. Previous work demonstrated that the poly(ortho-phenylenevinylene) design could have high-spin coupling along the polymer backbone even in the presence of defects. Consideration of these examples led to the design including a paramagnetic, chelating ligand as the spin-containing unit. These polymers will be among the first organic polymers having high-spin coupling along the main chain and also containing structural units for controlling interchain interaction. Future work will prepared extended solids from these polymers. These extended solids may be thought of as infinitely crosslinked polymers have a main-chain paramagnetic repeat unit.; The semiquinone, paramagnetic chelating ligand, was generated by bulk electrolysis. EPR experiments showed high-spin state in these polymers. Curie plots from VT-EPR experiments all showed straight lines of the doubly-integrated {dollar}Delta msb{lcub}s{rcub}{dollar} = 2 signal which is consistent with {dollar}Jge0{dollar} and ferromagnetic coupling along the polymer chain.; Antiferromagnetic coupling along the poly(ortho-phenyleneethynylene) as the number of electrons per repeat unit increased, was envisioned. No evidence of antiferromagnetic coupling was observed due to precipitation during bulk electrolysis.