本篇論文探討具有雙自由基性質多環芳香烴化合物的合成及結構與性質分析。在內容中主要分為兩部分：二茚并[2,1-f:1',2'-j]苉化合物合成與性質分析、二茚并[c, j]二苯并[a,h]蒽合成探討。
第一部分為二茚并[2,1-f:1',2'-j]苉化合物合成與性質分析，利用有機全合成方法，合成出多環芳香烴5,14-雙(2,4,6-三甲苯基)二茚并[2,1-f:1',2'-j]苉(P1)與5,14-雙(2,4,6-三甲氧基苯基)二茚并[2,1-f:1',2'-j]苉(P3)。首先利用X-ray單晶繞射了解二茚并[2,1-f:1',2'-j]苉化合物結構特性，發現該化合物具有螺旋結構與螺旋烴相似。為了證明其具有雙自由基性質我們進行電子自旋共振光譜儀實驗，在光譜中具有明顯的訊號，化合物P1的g因子(g-factor)為2.00306。之後利用變溫核磁共振光譜與超導量子干涉實驗瞭解雙自由基電子自旋組態單重態與三重態能階差異，化合物P1從變溫1H NMR實驗中可以發現在高溫光譜中訊號會變寬甚至消失，代表雙自由基因加熱由反磁性的單重態基態轉變成順磁性三重態激發態。化合物P1超導量子干涉實驗量測其雙自由基磁化率隨溫度變化數據，並利用Bleaney-Bowers公式擬合，計算出單重態與三重態能隙為-1.83 kcal．mol-1。最後利用紫外-可見光譜與循環伏安法分析化合物P1、P3之光化學與電化學性質，並估算最高電子佔有分子軌域(HOMO)及最低電子未佔有分子軌域(LUMO)能隙。
第二部分是二茚并[c, j]二苯并[a,h]蒽合成探討，目標利用有機全合成出多環芳香烴9,19-雙(2,4,6-三甲苯基)二茚并[c, j]二苯并[a,h]蒽(P2)。雖然能夠成功合成出前驅物9,19-雙(2,4,6-三甲苯基)-9,19-二氫二茚并[c, j]二苯并[a,h]蒽但是在隨後利用叔丁醇鉀、二甲基甲醯胺催化的氧化脫氫反應中，反應結果複雜難以利用矽膠管柱層析或再結晶法將產物純化。推測可能是因為目標產物P2具有較強的雙自由基性質反應性活潑易與氧或是其他分子反應，導致反應結果不盡理想。最後嘗試改以2,3-二氯-5,6-二氰對苯醌（DDQ）作為氧化脫氫反應之氧化劑，但是效果也不佳。未來若是要合成二茚并[c, j]二苯并[a,h]蒽類的化合物，其穩定性是首要考慮的問題，或許能夠在結構中加入其他官能基增加其穩定度，增加合成上的成功率。

Polycyclic aromatic hydrocarbons that exhibit a biradical character have been researched for many years, and their special properties have fascinated chemists for a long time. In this study, syntheses of three kinds of biradicaloid polycyclic aromatic hydrocarbons were reported.
In part I, polycyclic aromatic hydrocarbons 5,14-dimesityldiindeno[2,1-f:1',2'-j]picene P1 and 5,14-bis(2,4,6-trimethoxyphenyl)diindeno[2,1-f:1',2'-j]picene P3, which exhibit biradical character, were synthesized and characterized. Their structural properties and aromaticity were revealed by X-ray crystallography. Notably, the structure of the diindeno[2,1-f:1',2'-j]picene derivatives is very similar to that of helicenes. We then investigated the biradical magnetic property of the compound P1 by electron spin resonance (ESR), variable-temperature 1H nuclear magnetic resonance (VT-1H NMR), and superconducting quantum interference device (SQUID). Finally, their photophysical and electrochemical properties were measured by UV-vis spectroscopy and cyclic voltammetry.
In part II, we attempted to synthesize 9,19-dimesityldiindeno[c, j]dibenzo[a,h]anthracene P2, which perhaps has a higher biradical character than P1 and P3. We used five steps to synthesize the precursor of P2, 9,19-dimesityl-9,19-dihydrodiindeno[c,j]- dibenzo[a,h]anthracene; however, the following oxidative dehydrogenation was unsuccessful. Although we could observe the signals of P2 in the QTOF MS spectrum, it was difficult to purify P2 by silica gel chromatography or recrystallization. Presumably, the compound P2 has a very strong biradical character, making it too unstable to be purified under ambient conditions.

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