Synthesis and characterization of zero and first generation organometallic nanorods /

Abstract

There is substantial interest in new materials exhibiting one, two, and threedimensional structures that are patterned on the nanoscale. Such organometallic materials have potential use in electronics, photonics, and nonlinear optical applications. The complexes discussed in this thesis were designed to have thermally and chemically stable repeating units such as [trans-Mo(PhzPCHzCHzPPhz)z(Il-CN-l,4-C6H4-NC)]. Isonitrile-bridged species have valuable features such that there is substantial conjugation down the oligomer backbone and because they form strong complexes with rationally tunable bonding characteristics. The aromatic isonitriles were prepared by reacting the aromatic amines with formic acid and then dehydrating the resulting formamides with trichloromethylchloroformate. The phosphine ancillary ligands were prepared by Grignard reactions and allow the nanorod's steric and electronic properties to be varied independently of one another. The phosphine ligands were reacted in the presence of MoCl5 to form the desired dinitrogen complexes. The monomers and oligomers were prepared by condensation reactions between the un-complexed bifunctional isonitriles and Mo(PR3)4(Nz)z moieties. After synthesizing the nanorods of the desired length, they were capped on each end using the terminal organometallic groups such as, Cr(CO)5 and CpFe(CO)/.