Research On The Complexes Constructed By Ferrocenyl Carboxylate

The ferrocenyl carboxylate were synthesized some years ago, but their coordination properties have not been intensively explored. In fact, as a ligand, ferrocenyl carboxylate has many advantages: the versatile coordination modes of the carboxylate group make the self-assembly of crystal engineering easily available. Furthermore, the incorporation of the ferrocenyl moiety into the metal-organic frameworks can combine the organometallic with coordination chemistry, and provide an effective way to prepare new functional materials with unique features besides the merits of organometallic and coordination complexes, which can be used in the field of electrical, magnetic, preceramic and catalytic, and nonlinear optical (NLO) aspects. On these bases, introducing bulky ferrocenyl carboxylate groups into the polymeric chemistry and further exploiting the relationship between their structures and properties have become one of the most attractive research fields in modern material chemistry.In this paper, several novel metal-organic polymers and some heterometallic complexes were obtained by treating ferrocenylbenzoate (FcC6H4COONa), β-ferrocenylacrylate (FcCH=CHCOONa) or ferrocenethiocarboxylate (FcCOSNa) (Fc=(η~5-C5H5)Fe(η~5-C5H4) with some metal ions directly or under the help of some subsidiary ligands. Additional, their syntheses, structural analyses, redox properties, thermal stabilities, magnetism, catalysis activity and third-order nonlinear optical properties (NLO) were also investigated.Firstly, treatment of p-HOOCH4C6Fc with Mn(OAc)2 2H2O or Cd(OAc)2 2H2O afforded two similar one-dimensional linear chain polymers 1 and 2, double-bridge polymer 3 and a ladder-like framework 4. Polymers 1-3 behave as ID Heisenberg Mn(II) chain with intrachain antiferromagnetic interaction between the local high-spin Mn(II) ions, the exchange coupling parameters J are larger than most of the reported di-Mn(II) complexes which containing μ2-aqua and μ2-carboxylato units and some one-dimensional Mn(II) carboxylic polymers. And we also obtained a novel one-dimensional zigzag chain polymer 5 by the reaction of o-HOOCH4C6Fc with Zn(OAc)2 and a subsidiary ligand bpe. The determinations of third-order nonlinear optical (NLO) properties show that all these polymers possess strong NLO self-focusing effects.Secondly, zero-dimensional polymer 6, .one-dimensional chain polymers 7, 8, two-dimensional hybrid polymer 9 and two heterometallic complexes 10 and 11 were preparedby the reaction of FcCH=CHCOONa with proper metal salts or under the help of organic subsidiary ligands. The structure of polymer 6 shows a giant scroll-wheel-like arrangement of the eight /?-OOCCH=CHFc units in four kinds of coordination modes with a presumed Pb6 octahedron core. In 7 and 8, /?-OOCCH=CHFc units connect the metal ions into two 1-D polymers by mono-atomic bridging mode and tridentate bridging mode, respectively. 9 is the first example of 2-D polymers which containing ferrocenyl caroxylate and organic subsidiary ligand, simultaneously. The third-order NLO properties' determination shows that these polymers all exhibit stronger self-focusing effects than the heterometallic complexes and the corresponding ligand.Thirdly, based on FcCel^COONa, six heterometallic complexes 12~17 were synthesized. The steric hindrances of the chelating ligands make these complexes hard to form polymeric complexes. The results of third-order NLO studies show that the hyperpolarizability /values of these complexes are close to those of the corresponding ligands. We also investigated the catalysis activity of the ferrocenylbenzoate-based heterometallic complexes on oxidation of benzoic alcohol to benzaldehyde with 30% aqueous hydrogen peroxide as oxygen donor. The result shows that these complexes all exhibit some catalytic behavior in this reaction.Fourthly, no literatures have touched on the syntheses and structures of ferrocenethiocarboxylate-based polymeric complexes till now. Treated FcCSONa with different metal ions with the help of some subsidiary ligands, we gained two novel one-dimensional Cd(II) polymers 18 ^ 19 and one heterometallic complex 20. In polymer 18, FcCOS" units connect the adjacent Cd(II) ions through mono-S-atomic bridge into dimmers, these dimmers are joined together by 4,4'-bpy to form a 1-D double-bridge chain. While in polymer 19, Cd(II) ions are connected by bbp into 1-D zigzag chain, the FcCOS~ groups just hanging on the main chain formed by Cd bbp Cd bbp .Finally, we designed and synthesized several bispyridine ligands. Based on these ligands, we obtained one 1-D zigzag polymer 20, binuclear metallamacrocycle 21, two double-stranded 1-D polymers 22 and 23. Additional, one hybrid polymer 25 constituted by en, 4,4'-bpy and Cd(NO3)2-H2O was also obtained. These polymers' third-order NLO determinations show that they all possess good nonlinear optical refraction effects, which indicate this kind of polymers is one of an excellent candidates in designing optical materials.