The Design, Synthesis And Magnetic Properties Of Novel Containing 1,10-phenanthroline Polymers And Their Metal Complexes

Organic and polymeric magnetic materials have been studied extensively, and a great progress has been achieved in this field. Now it is one of the research focuses of chemisty, physics and materials science. Compared with traditional magnets, the magnetic polymers have characteristics of structural diversities, low density, low magnetic loss, and easy processing.In our paper, seven kinds of novel containing 1,10-phenanthroline polymers and their corresponding metal complexes are designed and synthesized, and the magnetic behaviors of these complexes were studies. We investigated for the relationship of the structure of polymer complex and the magnetic property of the corresponding complexes through synthesis of various structures of magnetic materials in order to find high Tc metal complexes.Three kinds of monomers, that is,5,6-diamino-1,10-phenanthroline,4,7-diamino-1,10-phenanthroline and 4,7-bis(4-aminophenoxy)-1,10-phenanthroline have been synthesized from different routes. Among them,4,7-bis(4-aminophenoxy)-1,10-phenanthroline hasn't been reported before, which was a new compound. Moreover, we have developed a novel and efficient process for the formation of phendione from 1,10-phenanthroline. This method is conducted under mild conditions and is suitable for scale-up, which makes it an attractive alternative for the synthesis of this class of molecules.Seven kinds of polymers have been prepared in the paper. The benzene-containing polymer (DAPcTPA and DAPcIPA) was synthesized by polycondensation of 5,6-diamino-1,10-phenanthroline (DAP) and terephthalaldehyde (TPA)(or isophthalaldehyde (IPA)). The pyridine-containing polymer (DAPcPYA) was prepared by polycondensation of 5,6-diamino-1,10-phenanthroline (DAP) and 2,6-pyridinedicarboxaldehyde (PYA). The fully conjugated poly (Schiff base) (DAPcDOD) was synthesized by polycondensation of 2,7-dimethyl-2,4,6-octatriene-1,8-dial (DOD) with 5,6-diamine-1,10-phenanthroline (DAP). The poly(amic acid) (PPHPA) was synthesized by the polycondensation of 4,4'-oxydiphthalic dianhydride (ODPA) with 5,6-diamine-1,10-phenanthroline (DAP). The diphenyl-containing polymers (PPDBP and PPHBP) were synthesized by polycondensation of Biphenyl-4,4'-dicarbaldehyde (BP) and 4,7-diamine-1,10-phenanthroline (PD) or 4,7-bis(4-aminophenoxy)-1,10-phenanthroline (PH) respectively. And then, the metal complexes of these polymers were prepared. The structures of the polymers and the corresponding complexes were determined by FT-IR,1H NMR and element analysis. The metal contents were measured by complexometric titration.The magnetic properties of these complexes were examined as a function of magnetic field strength at 5 K and as a function of temperature (5-300 K) at magnetic field strength of 30 kOe with a physical properties measurement system (PPMS-9T) magnetometer (QUANTUM DESIGN). DAPcTPA-Ni2+, DAPcTPA-Co2+, DAPcIPA-Ni2+ and DAPcIPA-Co2+ exhibit soft ferromagnetism, while DAPcTPA-Fe2+ and DAPcIPA-Fe2+ are antiferromagnets. Both DAPcPYA-Ni2+ and DAPcPYA-Nd3+ exhibit the characteristic of soft-magnetic materials at low temperature, the Curie-Weiss temperature are 117 K and 102 K, respectively, while DAPcPYA-Fe2+ was antiferromagnet too. The fully conjugated poly (Schiff base) (DAPcDOD) complexes, DAPCDOD-Ni2+ and DAPCDOD-Co2+ were soft ferromagnets, the Curie-Weiss temperature are 48 K and 81 K but DAPCDOD-Fe2+ was antiferromagnet. The poly(amic acid) (PPHPA) complexes, PPHPA-Ni2+ and PPHPA-Nd3+ exhibit the characteristic of soft-magnetic materials at low temperature, the Curie-Weiss temperature are 20 K and 75 K, respectively, while PPHPA-Cu2+ exhibits antiferromagnetic interaction.The magnetic properties of containing 4,7-disubstituted-1,10-phenanthroline complexes were examined, too. Both PPDBP-Ni2+ and PPHBP-Ni2+ exhibit antiferromagnetic properties. By comparing the magnetic properties of the different metal complexes, we found that the magnetic properties of complexes effected by the structure of ligand and the kinds of metal.