以苯並噻二唑雙?啶與芳香多酸製備金屬有機框架化合物：
合成、結構鑑定、氣體吸附及染料移除

本研究透過鈴木偶聯反應合成出新穎有機配體苯並噻二唑雙?啶(Bis(pyridin-4-yl)benzothiadiazole，BTD-bpy)，再利用此有機配體與不同的金屬鹽及芳香多酸化合物透過溶劑熱合成法製備出五個金屬有機框架化合物，分別為[Co2(Hbtc)2(BTD-bpy)2] (1，H3btc = Benzene-1,3,5-tricarboxylic acid，金屬來源：Co(NO3)2)、[Zn2(BTD-bpy)(Hbtc)2(MeOH)2] (2，金屬來源：Zn(NO3)2)、[Zn4(BTD-bpy)2(1,4-ndc)4] (3，1,4-H2ndc = 1,4-Naphthalenedicarboxylic acid，金屬來源：Zn(NO3)2)、Mn5(BTD-bpy)2(1,4-ndc)5(MeOH)2 (4，金屬來源：Mn(ClO4)2)及[Ni2(BTD-bpy)(NO2-1,4-bdc)2(MeOH)] (5，NO2-1,4-H2bdc = 2-Nitrobenzene-1,4-dicarboxylic acid，金屬來源：Ni(NO3)2)。化合物1為二維層狀結構，層與層間以互相平行的方式堆疊並形成微孔通道，孔隙率為19.5%。化合物2為二維層狀結構，層與層間以AAA方式堆疊並無形成微孔通道。化合物3為三維簡單立方之層柱狀結構，有二次互穿的現象，孔隙率為19.8%。化合物4具有兩種不同的多核金屬團簇建構單元，形成三維網狀結構。化合物5為二維格子狀之層狀結構，具有2D+2D→3D的互穿結構特性。從溶液相單一染料分子移除實驗中可以發現化合物1對AO7、MO有優良的移除能力，推測為化合物1利用BTD-bpy上的孤對電子以靜電吸引力吸附靜電負性染料之相對陽離子後，此相對陽離子再吸引已解離之電負性染料而產生吸附效果，電正性染料則由於帶正電的部分無法有效和前述之孤對電子接觸而沒有移除效果；化合物2對AO7有優良的移除能力，推測為結構中的BTD-bpy和AO7產生氫鍵所致；化合物3對AO7、MO、MyB有優良的移除能力，推測原因則與化合物1相同；化合物4則未對任何染料分子表現出明顯的移除效果，進一步的混合染料分子移除實驗中，可以發現化合物1在MB/MO、MG/AO7、MG/MO、RhB/AO7、RhB/MO等染料混合水溶液中對MO、AO7有選擇性移除的效果；化合物2在 MG/AO7染料混合水溶液中對AO7有選擇性移除的效果；化合物3在MB/AO7、MG/AO7、MG/MO、RhB/AO7、RhB/MO、RhB/MyB等染料混合水溶液中對MO、AO7、MyB有選擇性移除的效果。將化合物1-4置於碘之環己烷溶液中進行吸附實驗，雖然溶液顏色無明顯變淡，但晶體顏色有變深的傾向，說明化合物1-4可吸附碘分子。此外，脫附實驗亦證明此一現象。同時我們也對化合物1進行二氧化碳之吸附能力相關的實驗，結果顯示化合物1對二氧化碳吸附效果不佳。

關鍵字

配位聚合物；染料分子移除；二氧化碳

並列摘要

A new organic ligand bis(pyridin-4-yl)benzothiadiazole (BTD-bpy) was synthesized by Suzuki-coupling, which was used to assemble with metal ion and aromatic multicarboxylic acid to form five new metal—organic frameworks (MOFs), namely [Co2(Hbtc)2(BTD-bpy)2] (1, H3btc = benzene-1,3,5-tricarboxylic acid), [Zn2(BTD-bpy)(Hbtc)2(MeOH)2] (2), [Zn4(BTD-bpy)2(1,4-ndc)4] (3, 1,4-H2ndc = 1,4-naphthalenedicarboxylic acid), Mn5(BTD-bpy)2(1,4-ndc)5(MeOH)2 (4), and [Ni2(BTD-bpy)(NO2-1,4-bdc)2(MeOH)] (5, NO2-1,4-H2bdc = 2-nitrobenzene-1,4-dicarboxylic acid), under solvothermal conditions. Compound 1 has a 2D layer structure; these 2D layer structures are parallel stacked to form open channels with porosity of 19.5%. Compound 2 shows a 2D layer structure; these 2D layers are arranged in an AAA manner. Compound 3 has 2-fold interpenetrated 3D primitive cubic (pcu) type pillared-layer frameworks, with porosity of 19.8%. Compound 4 has a 3D network structure constructed from trinuclear and dinuclear metal clusters. Compound 5 has a 2D grid-like layer structure, showing 2D+2D→3D interpenetration. The single-dye removal experiments on Acid Orange 7 (AO7), Malachite Green (MG), Methylene Blue (MB), Methyl Orange (MO), Methyl Blue (MyB), and Rhodamine B (RhB) showed that 1 could adsorptively remove AO7 and MO from water, 2 could remove AO7, and 3 could remove AO7, MO, and MyB, whilst 4 couldn’t remove dye materials effectively. Moreover, 1 could selectively remove AO7 and MO from dye mixing solutions of MB/MO, MG/AO7, MG/MO, RhB/AO7, and RhB/MO, 2 could selectively remove AO7 from dye mixing solution of MG/AO7, and 3 could selectively remove AO7, MO and MyB from dye mixing solutions of MB/AO7, MG/AO7, MG/MO, RhB/AO7, RhB/MO, and RhB/MyB. In iodide adsorption test in cyclohexane solution, 1-4 ineffectively adsorb iodide molecules, as supported by crystal color change and further confirmed by I2-releasing studies in methanol. We further investigated the sorption behavior of 1 toward carbon dioxide, which displayed poor uptake ability of 61.8 cm3/g at 195 K and p/po = 1.