| 摘要: | 分子的發光基團決定了其紫外-可見光吸收的波段，也使得互補波段透射或反射出來。多環芳香碳氫化合物(PAHs)，可以看成為石墨的一個小單位，能利用在各種不同的有機電子元件上。PAHs 的芳香環上，如含有氮或氧異原子，會有特殊的化學或物理性質。
本論文使用醋酸銅或鈀(Pd/C)的金屬催化，使BINOL 成功轉化成peri-Xanthenoxanthene (PXX)，具有藍色螢光。文獻中曾有人使用氧化劑TCNQ 對PXX 加以改質，但並未深入對其他氧化劑進行研究。我們使用碘、溴等不同氧化劑進行反應，發現PXX 與碘反應會氧化產生自由基陽離子；N,N-二甲基苯胺則能進行逆反應，將氧化後的自由基陽離子還原回PXX，我們並利用核磁共振光譜觀察反應行為。
如使用溴，會發生親電性取代反應，形成Br-PXX，而不是自由基陽離子，Br-PXX 不再被碘氧化。Br-PXX 行C-C 偶合反應，可以合成出新的Ar3N-PXX 衍生化合物，則又可被碘氧化。
A chomophore is the part of a molecule responsible for its color, i.e., absorbing certain UV-Vis wavelengths and transmitting or reflecting the complimentary wavelengths. In this dissertation, the chromophore of interest has a π-conjugated polycyclic aromatic system with heteroatoms in skeleton. Large polycyclic aromatic hydrocarbons (PAHs), as subunits of graphene, have been exploited in various organic electronic devices. PAHs containing N or O heteroatoms in the aromatic framework exhibit unprecedented chemical and physical properties.
In this thesis, the use of Cu(acetate) and Pd/C as metal catalyst successfully transformed BINOL to blue fluorescent peri-Xanthenoxanthene (PXX). In the literature TCNQ was reported to oxidize PXX into (PXX)(TCNQ). Yet not many else oxidants were studied. As a broadening effort, the study herein utilizes iodine, bromine, and other oxidants to react with PXX. PXX was found to react with iodine to produce a radical cation, while N,N-dimethylaniline is able to realize the reverse reaction to bring back the PXX. 1H NMR, UV-Vis, and fluorescence spectroscopies were used to investigate characteristics of the reaction, Bromine reaction with PXX proceeds with electrophilic substitution to form Br-PXX, not any more a radical cation. Br-PXX could not be oxidized by iodine. With a cross coupling C-C bond formation reaction, Br-PXX was transformed to a new Ar3N-PXX derivative that interestingly could be oxidized with iodine. |
