以D-樟腦酸根製備有機金屬框架化合物之自組裝合成、結構鑑定與性質探討

本論文利用D-樟腦酸 (D-camphorate acid, D-H2cam)、1,3-二(4-呲啶)丙烷(4,4′-trimethylenedipyridine, TMDPy)、K2CO3與二價鋅、鎘金屬離子以及三價銪金屬離子在含有DMAc和H2O混合溶液下進行溶劑熱反應，合成四種金屬有機骨架結構 [Zn(D-cam)(TMDPy)･2H2O] (1)、[Cd(D-cam)(TMDPy)･2H2O] (2)、[Cd(D-cam)(TMDPy)] (3)和[Eu(D-cam)(OAc)(H2O)] (4)，進而探討其固態結構及物理性質。化合物1跟2都具有孔洞特性的三維三次互穿鑽石型結構。化合物3與化合物2結構組成相同，也是具有孔洞特性的鑽石型結構，但為[2+2]形式之四次互穿。控制鎘金屬鹽的陰離子種類(NO3-，OAc-)、溶劑熱反應時間(48或72小時)以及反應製程可有效地分別合成出化合物2與化合物3。本論文我們研究化合物1和化合物2對甲基橙 (Methyl Orange, MO)、甲基藍 (Methyl Blue) 和MO/ Methyl Blue 混合染料以及亞甲藍(Methylene Blue, MB)染料的吸附能力。經由實驗結果顯示化合物1和化合物2對Methyl Blue有吸附能力，並且在MO/Methyl Blue 混合物中具有選擇性。最後，本論文以化合物4進行陽離子置換反應，但化合物4之中心銪金屬無法被三價鋱金屬離子所取代。

關鍵字

超分子化學；金屬有機骨架化合物；溶劑熱合成法；染料吸附

並列摘要

Reactions of D-camphoric acid (D-H2cam), 4,4′-trimethylenedipyridine (TMDPy), K2CO3, and metal salt (Zn(OAc)2, Cd(NO3)2, Cd(OAc)2, and EuCl3 ) in a N,N- dimethylacetamide (DMAc)−H2O media under hydro(solvo)thermal conditions afforded four metal−organic frameworks [M(D-cam)(TMDPy)･2H2O] (1, M = Zn; 2, M = Cd)、[Cd(D-cam)(TMDPy)] (3), and [Eu(D-cam)(OAc)(H2O)] (4). Compounds 1 and 2 have identical crystal structures that feature a 3-fold interpenetrating diamondoid net. Compound 3 also has a diamondoid crystal structure, but in an abnormal [2+2] 4-fold interpenetration. Controlling the anion (NO3- or OAc-) of cadmium salt, the reaction time (48 or 72 hrs), and reaction procedure can efficiently produce compound 2 and compound 3 separately. We have studied the adsorption abilities of compounds 1 and 2 toward methyl orange (MO), methyl blue, and methylene blue (MB) dyes. As a representative, both of them show uptake for methyl blue and can selectively bind methyl blue over MO. Further, we have also studied the cation-exchange property of compound 4, which unfortunately did not occur by using Tb3+ to replace Eu3+.