(I) Self-Assembly, Spectroscopic, and Anion-Exchange Studies of d10-Metal [Zn(II), Cd(II) and Cu(I)] Complexes Containing C3-Symmetry Ligands (II) Structures, Spectroscopic and Luminescence Properties of Dinuclear Pd(II) and Pt(II) Complexes w

• Main Authors: Tse-hao Chiu, 邱則豪
• Other Authors: Biing-Chiau Tzeng
• Format: Others
• Language: zh-TW
• Online Access: http://ndltd.ncl.edu.tw/handle/17863973571623250923

碩士 === 國立中正大學 === 化學所 === 95 === Abstract The research described in this thesis was classified into two parts. In the first part, we have successful synthesized a 3-D porous coordination polymer {[Cd(L1)2](ClO4)2}n (1a) and two 2-D coordination polymers [Zn2(L1)2(NO3)3H2O]n (2) and [CuI(L2'')]n (3) by using tripodal ligands L1 and L2'' (L1 = N,N'',N"-tris(4-pyridinyl)-1,3,5-benzenetricarboxamide, L2'' = N,N'',N"-tris(3-pyridinylmethyl)- 1,3,5-benzenetricarboxamide). All the compounds are structurally characterized by the single crystal X-ray diffraction study. The anion-exchange product 1a was obtained from the 3-D coordination polymer {[Cd(L1)2]Cl2}n (1) through the single- crystal to single-crystal exchange process. 1a, 2 and 3 are all luminescent in the solid state with emission maxima at 513nm, 458nm, and 510nm respect- tively. The emission of 1a could be tentatively assigned as an MLCT (metal-to-ligand charge-transfer) transition mixing with an IL (intraligand) transition, whereas 2 is suggested due to an IL transition. The emission origin of 3 may be attributed to an XLCT (halide-to-ligand charge-transfer) transition. In the second part, we synthesized and characterized a series of dinuclear Pd(II) and Pt(II) compounds [{Pd(d-t-bpy)(NS2)}2][PF6]2(4), anti-[{Pt(d-t-bpy)(NS2)}2][ClO4]2(5), and syn-[{Pt(d-t-bpy)(NS2)}2][ClO4]2 (6) (NS2=C7H4NS2-, d-t-bpy=4,4''-di-tert-butyl-2,2''-bipyridine).Thedinuclear Pt(II) complexs have been isolated in two crystal forms, an orange syn-form (6) and a yellow anti-form (5), which show distinct luminescence properties. The intramolecular metal×××metal distances of 4, 5, and 6 are 2.951(4), 2.973(1), and 2.973(4), respectively. Impor- tantly, 6 has also an intermoleculat Pt×××Pt contact of 3.859 in the crystal packing. We also synthesized a mono-nuclear Pt(II) compound [Pt(d-t-bpy)(NS2)2] (7), expected to have no Pt×××Pt interaction, for the comparison purpose. All the platinum complexes show photoluminescence in the solid state, whereas the palladium complex 4 is non-emissive. 5 and 6 exhibit intense yellow and orange luminescence at room temperature, respec- tively. When the temperature was lowered to 77K, both 5 and 6 showed a red shift in emission energy, where 6 shows a more pronounced effect and this phenomenon was suggested to an intermoleculat Pt×××Pt inter- actions of 6. The emission origin of dinuclear Pt(II) complexes may be attributed to an LMMCT (ligand-to-metal-metal charge-transfer transi- tion), significantly influenced by an intermolecular Pt×××Pt interaction.