Self-Assembly , Characterization and Host-Guest Interaction of Nanoscale Rhenium (I) Rectangles

• Main Authors: Woei-Chyan Yang, 楊偉權
• Other Authors: 曾添文
• Format: Others
• Language: zh-TW
• Published: 2003
• Online Access: http://ndltd.ncl.edu.tw/handle/86961381028863879440

碩士 === 國立臺北科技大學 === 化學工程系碩士班 === 91 === Abstract： key words: self-assembly, supramolecules, host-guest interaction. In the first of this thesis, the rational design and synthesis of self-assembled rhenium-based rectangular boxes has been performed. Characterization by single- crystal X-ray diffraction, NMR, and UV-visible analyses have been carried out. Their molecular recognition property has been examined. The second research topic concerns with the copper-mediated catalytic transformation of organic compounds at ambient temperature. （I）Synthesis of Novel Rectangular Supramolecules The synthesis and characterization of novel rectangular host-guest supramolecules are reported. The self-assembly of rhenium-based nanohost with a rectangular inner cavity can be achieved via a simple one-step synthetic route. The rational selection of fac-(CO)3Re as corners, the judicial choice of a chelating three-electron donor, chloranilic acid (CA), and a two-electron donor, 4, 4’-bipyridyl (bpy), or, trans-1, 2 bis(4-prydyl)-ethylene (bpe) as a spacer bridging ligand can fulfill the eighteen-electron configuration around the rhenium center. As a result, self-assembly of novel molecular rectangle possessing a large cavity could be obtained instead of two thermodynamically favored molecular squares. Three rectangular supramolecular nanohosts: Re4(CA)2(bpy)2•(p-xylene)2 (1.1), Re4(CA)2(bpy)2•(mesitylene) (1.2) and Re4(CA)2(bpy)2•(THF)4 (3) have been successfully prepared and characterized. Their structures have been analyzed by X- ray crystallography. Crystal data for 1.1: space group P , a = 9.884(1) Å, b = 13.020(1) Å, c = 13.739(1) Å, α = 106.13(4), β = 105.95(5), γ = 96.56(5), V = 1597.95(2) Å3, Z = 1. Crystal data for 1.2: space group P21/n, a = 11.020(2) Å, b = 18.442(5) Å, c = 14.944(4) Å, α = 90.00, β = 104.02(11), γ = 90.00, V = 2946.75(12) Å3, Z = 2. Crystal data for 3: space group C2/m, a = 17.660(9) Å, b = 25.049(15) Å, c = 10.907(6) Å, α = 90.00, β = 120.95(3), γ = 90.00, V = 4137.9(4) Å3, Z = 2. （II） Catalytic transformation of a organic compound catalyzed by Cu(II), Ni(II) at ambient temperature A one-step Cu(II)-catalyzed transformation of organic compound 3,6-di-2-pyridyl-4-{[(2-pyridyl)carbonyldiazenyl]-(2-pyridyl)methyl}-1H-1,2,4,5-tetrazine （4） has been achieved at ambient temperature by using 3,6-Di-2-pyridyl-1,2,4,5-tetrazine（DPTZ） as starting material. In addition to Cu(II) ion, Ni(II) is also capable of mediating the chemical transformation of DPTZ molecule. The plausible self-assembly catalytic reaction has been purposed reasonably for compound 4. The molecular structure of 4 has been characterized by single-crystal X-ray diffraction analysis. The compound crystallizes in a triclinic crystal system with space group P , a = 7.9380(2) Å, b = 11.5280(4) Å, c = 12.0990(4) Å, α = 83.372(2)°, β = 86.127(2)°, γ = 77.4690(10)°, V = 1072.54 (6) Å3, Z = 2.