(I) Supramolecular Synthesis toward Molecular Triangles and Cages(II) Metal-Organic Coordination Polymers of 1,4,7,10-tetraaza- cyclododecane-1,4,7,10-tetrakis-pyridin-4-yl-amide

• Main Authors: Yun-Mei Lu, 陸勻美
• Other Authors: 曾炳墝
• Format: Others
• Language: zh-TW
• Published: 2005
• Online Access: http://ndltd.ncl.edu.tw/handle/09481621042059322720

碩士 === 國立中正大學 === 化學所 === 93 === The research focus in this thesis is classified into two parts. In the first part, we synthesize a series of dipyridyl dialkyl amides (1,4-bis[(3-pyridyl)ethynyl]benzene (L23’), 4,4’-diethynyl-4’’,4’’’- dipyridylbiphenyl (L24), 3,3’-diethynyl-4’’,4’’’-dipyridylbiphenyl (L24’)) and tripyridyl amides (N1,N3,N5-tri(pyridin-3-yl)benzene-1,3,5- tricarboxamide (L12’) ) as bridging ligands for the supramolecular synthesis. The long and rigid ligands L23’, L24, and L24’ are used in the construction of six molecular triangles via self-assembly with Pd(II) and Pt(II) ions as corners and d-t-bpy (4,4’-tert-butyl bipyridine) as ancillary ligands, [Pd(d-t-bpy)(L23’)]3(OTf)6 (1), [Pt(d-t-bpy)(L23’)]3(OTf)6 (2), [Pd(d-t-bpy)(L24)]3(OTf)6 (3), [Pt(d-t-bpy)(L24)](OTf)6 (4), [Pd(d-t-bpy) (L24’)]3(OTf)6 (5), and [Pt(d-t-bpy)(L24’)]3(OTf)6 (6). In addition, molecular cages, {[Pd(d-t-bpy)]3(L12’)2}(OTf)6 (7) and {[Pt(d-t-bpy)]3 (L12’)2}(OTf)6 (8), are constructed from the tripyridyl amide ligand L12’. Complexes 1-8 are isolated and characterized by electrospray ionization mass spectrometry, 1H NMR, and elemental analysis. In the second part, we design and synthesize a new tetrapyridyl amide ligand (1,4,7,10-tetraaza-cyclododecane-1,4,7,10-tetrakis-pyridin- 4-yl-amide (L13) ) as a bridging ligand for the synthesis of a series of cadmium(II) and zinc(II) coordination polymers, {[Cd(L13)(DMSO)2] Br2}n (9), {[Cd(L13)(DMSO)2]I2}n (10), {[Cd(L13) (DMSO)2](NO3)2}n (11), and {[Zn(L13)1/2(DMSO)]Br2}n (12). The X-ray diffraction analysis confirms that 9-11 are three-dimensional frameworks, and 12 two-dimensional one, where these four coordination polymers all show interesting one-dimension channels in the solid state. Finally, absorption and luminescence properties of 1-12 are also investigated in this thesis.