Studies of dipyridylamine derivatives : synthesis, structures, metal ion sensing and liquid crystal properties

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Title:	Studies of dipyridylamine derivatives : synthesis, structures, metal ion sensing and liquid crystal properties
Other Titles:	含氮橋基雙吡啶衍生物 : 合成、結構、金屬離子感測器與液晶性質研究
Authors:	高憲章;Kao, Hsien-chang
Contributors:	淡江大學化學學系博士班王文竹;Wang, Wen-jwu
Keywords:	1,10雙雜啡;鋅;螢光感測器;分子內電荷轉移;雙吡啶;離子液體;離子液晶;Zinc;Fluorescent Sensior;Intraligand charge-transfer;Dipyridylamine;Ionic liquid;Ionic liquid crystal
Date:	2010
Issue Date:	2010-09-23 16:12:56 (UTC+8)
Abstract:	本篇論文以1,10-雙雜菲(1,10-phenanthroline) 為架構，合成出類紫質開環配位子bis(1,10-phananthrolin-2-yl)amine (HDPA)，並對其物理化學性質進行分析，亦藉由HDPA是否質子化，調控反應物對架橋亞胺基或雜環氮進行修飾，作合成上之探討。由X-ray單晶結構解析，不同pH值環境下，HDPA可具饒曲transoid 及平面syn兩種結構。經氫核磁共振光譜研究顯示，調整pH值，HDPA的構形可因一罕見的分子內 CH•••N氫鍵，產生構形改變。理論計算結果發現，transoid 及平面syn兩種結構之熱焓值，僅差0.5 kcal mol-1，說明氫核磁共振光譜中所見現象，HDPA於溶液態中可進行兩種結構互換。 HDPA 與鋅離子反應可得HDPA的鋅錯合物[Zn(HDPA)(OAc)]。經x-ray單晶結構解析，因強烈π－π作用力影響，[Zn(HDPA)(OAc)]以雙聚體方式呈現於單晶結構中。於晶體堆疊方面，除了π－π作用力外，為使電荷平衡，[Zn(HDPA)(OAc)]亦與大陰離子 [Zn7(μ4-O)2(OAc)12]2-形成共結晶，而此七核鋅簇 [Zn7(μ4-O)2(OAc)12]2-是文獻中未曾被報導過的特殊陰離子。於紫外光-可見光譜中，[Zn(HDPA)(OAc)]的最低能量吸收峰可延伸至400 nm至500 nm，為的分子內電荷轉移吸收峰。發射光譜中，可以利用 385 nm 為激發波長，使[Zn(HDPA)(OAc)]在385 nm及580 nm產生雙發色光。其中，385 nm為配位子π－π的螢光，385 nm為架橋亞胺基nimine至配位子π的螢光。藉由以上光學特性，進而設計離子偵測實驗，發現 HDPA 對於鋅離子具專一偵測性，可作為良好的離子偵測器。 2,2-dipyridylamine 與不同碳數的溴烷反應,可得到一系列高純度具有離子液體特性的N,N’-dialkyl-2,2’-azapyridocyane (Cn-Dpya-X) 衍生物。由X-ray單晶結構分析可知，長碳鏈修飾在吡啶而非架橋亞胺基，並與BF4-共結晶，堆疊成為一層狀結構。以溴為陰離子的系列化合物中，短碳鏈的離子液體具有接近室溫的溶點，長碳鏈的化合物則具有熱致型離子液晶的特性；在偏光顯微鏡下可觀測到SmA的紋理圖。此系列離子液體在加入水後，可轉為層狀排列的濃致型離子液晶。 A family of acyclic aza-bridged bis-1,10-phenanthroline compounds has been synthesized in a convenient way. The resulting compounds 2 and 2•HCl were fully characterized and their solid-state structures and NMR spectroscopic properties were investigated to assess how the structural units affect the alkylation reactions. Solid state structure and NMR spectroscopic investigation reveal the transoid structure for 2. The broadening NMR peak in 2 is due to an unusual intramolecular CH…N hydrogen bond. The unique conformation provides an efficient and regioselective method to prepare the amino-substituted bis-2,2’-1,10-phenanthroline derivatives and 1,10-phenanthrolino-N-alkylated compounds. An aza-bridged bis-1,10-phenanthroline ligand HDPA was synthesized and observed to display a tetradentate coordination mode to form [Zn(HDPA)(OAc)]. The x-ray crystallography revealed the structure of [Zn(HDPA)(OAc)]2[Zn7(μ4-O)2(OAc)12], and the anion unit [Zn7(μ4-O)2(OAc)12]2- is the first case of a related structure of heptanuclear Zn(II) clusters. The compound then showed its lowest-energy transition assigned to ILCT band and displayed dual fluorescence with λmax = 385nm and 580 nm upon excitation at 325 nm. The emissions with λmax = 580 nm came from an intraligand 1(nimine-π*) excited state. The investigated fluorescence properties of HDPA associated with various metal ions indicated that the emission with λmax at 580 nm was more sensitive with Zn(II) than with other interfering cations. The synthesis and characterization of N,N’-dialkyl-2,2’-azapyridocyane (Cn-Dpya-X, n = 4, 8, 10, 12, 14, 16 and 18 for X = Br-, ClO4-, BF4-, NO3-) of ionic liquid series are reported. The x-ray crystallography revealed the structure of [C14-Dpya-BF4] and identified the lamellar packing. The short alkyl chains compounds (n = 4,8 and 10) exhibit liquid properties at room temperature. The ionic liquid crystalline behavior of Cn-Dpya-Br (n = 12,14,16,18) was investigated by means of differential scanning calorimetry, polarizing light optical microscopy and X-ray diffractometry. All these four compounds exhibit SmA mesophases when cooling from isotropic liquid. Addition of water to Cn-Dpya-Br (n = 14,16 and 18) is shown to result the lyotropic liquid crystal behaviors.
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