指導教授：金必耀臺灣大學：化學研究所郭珉翔Kuo, Min-ShiangMin-ShiangKuo2014-11-252018-07-102014-11-252018-07-102014http://ntur.lib.ntu.edu.tw//handle/246246/261353最近彭旭明教授與他的團隊成功合成出100％螺旋選擇性的金屬串分子，他們利用naphthyridyl-pyridyldiamine (npda)連接具有掌性的樟腦基團，成功地將頭基的掌性傳導到整個金屬串分子的螺旋選擇性上，本篇論文最主要的工作是以理論計算的方法去解釋上述的現象，計算方法是以半經驗法PM7與DFT的配合，其計算結果顯示金屬串分子的Δ和Λ螺旋形式之間的能量差距在我們的計算模型下超過氫鍵的能量，其原因是如果掌性芽基選擇了錯誤的螺旋形式，會造成強烈的立體障礙使其與穩定的螺旋形式能量有巨大的差距。 更進一步我們建立了金屬串分子的三核及四核假想模型，計算結果顯示要造成金屬串分子的螺旋選擇性，不只要其芽基具有掌性的頭基，並且其芽基的尾部的取代基團也需要相對的大以造成足夠的立體障礙，才能使得金屬串分子具有螺旋選擇性。Recently, Prof Peng, Shie-Ming and his coworkers have successfully synthesized 100% Δ and Λ forms of (Ni5((+)camnpda)4) by using ligands consisting of naphthyridyl-pyridyldiamine (npda) connected with chiral camphor groups. In this work, we investigate the influence the chiral camphor groups on the helicity of four ligands spiraling around the central nickel string by using DFT calculation and semiempircal PM7 method. Particularly, we show that the degeneracy of Δ and Λ forms of an EMAC complex will be removed by introducing a chiral substituent on each ligand. The results indicate that one of these two helical forms of surrounding ligands will be becomes energetically unfavorable by about 100 kcal/mol due to the strong steric repulsion between chiral camphor groups and hydrogens on neighbor naphthyridyl groups. We also construct hypothetical three core and four core EMACs then compare Δ and Λ forms of same chiral head group also shows that certain chiral head group fit certain helicity . Finally we make a conclusion that the position of chiral substituent is decided by its chirality and the helicity is decided by the position of head group(2-2 trans form) which can be a chiral group, combine those point of view, we can conclude that the helicity of EMACs can be control by chiral substituent of the head group .口試委員會審定書………………………………………………………………...…# 中文摘要……………………………………………………………………………….i 英文摘要……………………………………………………………………….……...ii 目錄………………………………………………………………….………………..iii 圖片列表………………………………………………………………………...……iv 表格列表…………………………………………………………………………...….v 一 螺旋選擇性金屬串分子發展…………………………………………………..1 二 半經驗計算方法(PM7)及密度泛函理論(DFT)介紹………………………….5 2-1 密度泛函論…………………………………………………………………...5 2-2 半經驗計算方法(PM7)……………………………………………………....6 三 螺旋選擇金屬串分子計算及分析…………………………………………….8 3-1 Ni5(camnpda)4之掌性配基對其螺旋選擇性之影響………………….….8 3-2 三核理論金屬分子串模型之掌性配基對其螺旋選擇性之影響……..…..18 3-3 三合理論金屬串分子模型之掌性配基對其螺旋選擇性之影響……………27 附錄………………………………………………………………………………….32 參考資料…………………………………………………………………………....3425397801 bytesapplication/pdf論文公開時間：2014/08/05論文使用權限：同意有償授權(權利金給回饋學校)螺旋性之影響thesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/261353/1/ntu-103-R01223162-1.pdf