Syntheses and Studies of Novel Tetradentate Nitrogen Ligands (Hnyqa) and Their Mixed Ligand Linear Tetranuclear Metal String Complexes

• Main Authors: Ya-Lun Hsu, 許亞倫
• Other Authors: 彭旭明
• Format: Others
• Language: zh-TW
• Published: 2007
• Online Access: http://ndltd.ncl.edu.tw/handle/14369351795743192341

碩士 === 國立臺灣大學 === 化學研究所 === 95 === The aim of this thesis is to investigate the synthesis, structures and properties of the new trinickel cluster, mononuclears and the new linear tetranickel complexes with two kinds of ligands, where the ligands are the three unsymmetrical ligands, 2-1,8-naphthyridyl-2’-inolinylamine (Hnyqa),N-(2-naphthalenyl)diaminodipyridine (H2npdpda), and N-(anisyl)diaminodipyridine (H2andpda). The three unsymmetrical ligands were synthesized by the palladium-catalyzed crosscoupling reaction. The ligands were characterized on the base of 1H NMR spectroscopy and mass spectrometry. [H2nyqa(ClO4)] (1), [Cu(μ2Hnyqa)2(MeOH)2](ClO4)2 (2), [Co(μ2-Hnyqa)2](BF4)2 (3), the new trinickel cluster [Ni3(nyqa)4Cl2] (4), [Ni4(μ4-npdpda)3(μ4-nyqa)(NCS)] (5) and[Ni4(μ4-andpda)3(μ4-nyqa)(NCS)] (6) were synthesized and characterized by X-ray crystallography. The framework of both complexes 5 and 6 are supported by two kinds of ligands. The magnetic susceptibility shows that complex 4 is ferromagnetic and the coupling constant is + 2.43 cm-1 and complexes 5 and 6 are paramagnetic. Cyclic voltammetrical data show that complexes 5 and 6 exhibits three quasireversible oxidation waves between 0.339-0.955 V. The complexes 1-6 were synthesized and characterized by X-ray crystallography, SQUID experiment and cyclic ammetrical method. The complex 4 is weak ferromagnetic; Complexes 5 and 6 can be easily oxidized. The oxidation potential (Eox) in complex 5 shifts to higher potential as compared with complex 6, because complex 6 have stronger electron donating function group than complex 5 .