Self-Assembly and Eletrochemical Sieving Studies of Luminescent Re(I)-Containing Cyclophanes

• Main Authors: Chen Yi-Chen, 陳怡甄
• Other Authors: 曾炳墝
• Format: Others
• Language: zh-TW
• Published: 2004
• Online Access: http://ndltd.ncl.edu.tw/handle/45942547721644451986

碩士 === 國立中正大學 === 化學研究所 === 92 === bstract The research focus in this thesis is classified into three parts. The first part is to utilize Py2S (4,4’- dipyridyl sulfide) and Py2S2 (4,4’- dipyridyl disulfide) as bridging ligands for the construction of neutral molecular loops, [Re(CO)3Cl(Py2S)]2 1 and [Re(CO)3Cl(Py2S2)]2 2. The one- dimensional channel structures with the cavity sizes of 6.8×6.8 Å2 (1) and 7.2×7.2 Å2 (2), respectively, have been confirmed by the X-ray diffraction studies, where the channel behavior is due to both ππ and non-classical hydrogen-bonding interactions. The second part is to utilize a series of designed pyridyl amides (L7-L10) as bridging ligands for the construction of molecular loops or squares with Re(I) as corner ions. The hydrogen-bonding functions of pyridyl amide may be anticipated to contribute in the formation of supramolecular nanotubes as functional materials by self-assembly. Fortunately, the crystal structure of complex 3, [ReL7]2, has been determined by an X-ray diffraction study, showing the channel structure based on the NH…CO hydrogen bonds. The spectroscopic and photophysical properties were also investigated. Complexes 1-7 studied here are weakly emissive, and this may be explained by the flexible backbone of the ligands. The loops 1 and 3 can be spin-coated on the glass electrode and dipped into an aqueous solution with various sizes of redox probes, and it is successfully demonstrated to show size exclusion based on the cavity sizes. This study shows that the porous nature of molecular materials may have potential applications in transportation or chemical sensing.