Study on the Self-Assembly of Transition Metal Supramolecular Materials Using Symmetrical and Asymmetrical Diaminodiamide Ligands

• Main Authors: Zi-yi Lin, 林姿宜
• Other Authors: Min-Shiun Chao
• Format: Others
• Language: zh-TW
• Published: 2014
• Online Access: http://ndltd.ncl.edu.tw/handle/32545589100065144299

碩士 === 國立勤益科技大學 === 化工與材料工程系 === 102 === Recently, supramolecular design, synthesis, and applications have been extensively studied. Transition metal complexes bearing nitrogen-containing ligands have many applications in biotechnology or industrial catalysis. In this thesis, we use Michael addition reaction to design and synthesize three kinds of diaminodiamide ligand that are 4,7-diazadecanediamide (L-2,2,2)、4-methyl-4,7-diazadecanediamide (4-Me-L-2,2,2)、4,7-dimethyl-4,7-diazadecane-diamide (4,7-Me2-L-2,2,2) and N,N’-bis(β-carbamoylethyl)1,2-diaminocyclohexane (BDC), respectively. We utilize these ligands with transition metal ions (Ni2+, Cu2+, Zn2+)to proceed self-assembly reaction, and through intermolecular hydrogen-bonding interactions to generate special supramolecular architecture. We use asymmetrical 4-Me-L-2,2,2 ligand with transition metal ions (Cu2+, Ni2+) to yield compounds [Cu(C12H26N5O3)(H2O)]‧(Cl)2 (1), [Cu(C9H20N4O2)(ClO4)2] (2), [Cu(C9H20N4O2)(NO3)‧NO3 (3), and [Ni(C12H26N5O3)(H2O)] ‧(Cl)2 (4), and then study these compounds’ different self-assembly reactions’ physical property. In these compounds [Cu(C12H26N5O3)(H2O)]‧(Cl)2 (1), [Cu(C9H20N4O2)(ClO4)2] (2), and [Cu(C9H20N4O2)(NO3)‧NO3 (3) investigate anion effect between the same ligand and different anions. We use symmetrical L-2,2,2 ligand with transition metal ions (Cu2+, Ni2+) to yield compounds [Cu(C8H18N4O2)(NO3)(H2O)]‧NO3 / [Cu(C8H18N4O2)(NO3)2]‧H2O (5), [Cu(C8H18N4O2)(SO4)] (6), and [Ni(C8H18N4O2)(NO3)]‧NO3 (7), and then study these compounds’ structure and physical property. We use symmetrical 4,7-Me2-L-2,2,2 ligand with transition metal ions (Cu2+) to yield compound [Cu(C10H24N4O2)] ‧(NO3)2 (8), and then study the compound’s structure and physical property. In the end, We use symmetrical BDC ligand with transition metal ions (Cu2+, Ni2+, Zn2+) to yield compounds [Ni(C12H24N4O2)(H2O)2] ‧(SO4)(9), [Cu(C12H24N4O2)(NO3)] (10), and [Zn(C12H24N4O2)(NO3)] ‧(NO3) (11), and then study these compounds’ structure and physical property. From compounds [Cu(C9H20N4O2)(NO3)‧NO3(3), [Cu(C8H18N4O2)(NO3)(H2O)]‧NO3 / [Cu(C8H18N4O2)(NO3)2]‧H2O (5), [Cu(C10H24N4O2)] ‧(NO3)2 (8), and [Cu(C12H24N4O2)(NO3)] (10), we investigate steric effect between the same metal and four different ligands. From compounds [Ni(C12H24N4O2)(H2O)2] ‧(SO4) (9), [Cu(C12H24N4O2)(NO3)] (10), and [Zn(C12H24N4O2)(NO3)] ‧(NO3) (11), we investigate metal effect between the same ligand and different metals. These compounds were structurally characterized by fourier transform infrared spectrometer and single-crystal X-ray diffraction method, and used diamond software to analyze spatial arrangement of self-assembly.