Synthesis, Characterization And Electrochemistry Of Manganese(â… ) Meso-substituted [14]tribenzotriphyrin(2.1.1) Complexes And Meso-substituted Dipyrromethene Nickel(â…¡) Complexes

[14]Triphyrin(2.1.1)(TriP) is a kind of subporphyrin which is contained three pyrrole rings that connected by meso-carbon bridges to form 14-Ï€ electronic aromatic conjugated system. Dipyrrolmethanes(Dipyrrin) are composed by two pyrrole rings and one meso-carbon which is an important precursor for the systhesis of porphyrin derivatives. [14]Triphyrin(2.1.1) and dipyrrolmethanes can provide unique metal complexation behaviour, which could result in novel applications, so they have attracted great attention. The research content mainly includes: 1) The synthesis of meso-aryl-substituted free-base [14]tribenzotriphyrin(2.1.1) complexes; 2) The synthesis and characterization of [(TriP)MnI(CO)3] metal complexes; 3) The synthesis of three different substituent of dipyrrolmethanes; 4) The synthesis and characterization of Ni(II)-Dipyrrin metal complexes(NiL2).Firstly, we synthesized four kinds of meso-aryl-substituted free-base [14]tribenzotriphyrin(2.1.1). Then we use TriP as ligand to react with manganese pentacarbonyl bromide to get four kinds of Manganese(I) TriP complexes([(TriP)MnI(CO)3]). Through X-ray analysis, to the molecular of Manganese(I) TriP complex, a dome shaped conformation is confirmed.As compare to the 1HNMR spectra of the synthesized [(TriP)MnI(CO)3], the NH proton of meso-aryl-substituted free-base TriP that comes up in the low field is no longer observed. This incidates that the N-H is replaced by Mn(I) ion.When the [(TriP)MnI(CO)3] were examined in CH2Cl2 containing 0.1 M TBAP as a supporting electrolyte at room temperature, the study illustrated when p-group(s) on the meso-phenyl rings is-CH3,-H or-F, two reversible one-electron reductions are observed for [TriPMnI(CO)3], while a third reduction step is observed for [TriPMnI(CO)3] when p-group on the meso-phenyl rings is-COOCH3. The electron donating-withdrawing properties of the para-substituents on the two meso-phenyl rings has small affect the chemical peaks of aromatic protons.We also systhesis a series of meso-substituted dipyrrin nickel(II) complexes. According to the single-crystal X-ray diffraction analysis and mass spectra of dipyrrin nickel(II) complexes, they are distorted tetrahedron conformation.The 1H NMR spectra of dipyrrin nickel(II) complexes shows that the electron donating-withdrawing properties of the para-substituents on the two meso-phenyl rings have great affect the chemical peaks of aromatic protons to the dipyrrin nickel(II) complexes.The electrochemical and spectroelectrochemical of dipyrrin nickel(II) complexes show that each compound undergoes an irreversible oxidation wave and two reversible one-electron reductions waves in CH2Cl2. While three irreversible oxidation wave and two or three reversible one-electron reductions waves in DMF. And according to the thin-layer UV/Vis spectra, the first reduction and the first oxidation reaction of NiL2 are both macrocycle-centered.