Tossing and turning: guests in the flexible frameworks of metal(III) dicarboxylates.
Tossing and turning: guests in the flexible frameworks of metal(III) dicarboxylates.
复制标题
翻来覆去：金属（III）二羧酸盐柔性框架中的客人。
作者：
Marie Vougo;Jin Huang;E. Anokhina;Xiqu Wang;A. Jacobson
在水热条件下得到了单晶Ga(OH)(C(8)H(4)O(4)).0.74C(8)H(6)O(4)(2)和Ga(OH，F)(C(8)H(4)O(4)).0.74C(8)H(6)O(4)(3)。2和3的结构与已报道的1，4-苯二甲酸铝(BDC)，Al(OH)(C(8)H(4)O(4)).0.7C(8)H(6)O(4)(1)具有相同的拓扑结构。骨架是通过将M-OH-M链(M=Al，Ga)与BDC阴离子相互连接形成大的菱形一维通道，填充额外的H(2)BDC客体分子占据通道中的无序位置。除去H(2)BDC后，可以插入其他客体分子，如H(2)O和吡啶。在这项工作中，我们研究了芳香族客体(BDC和吡啶)通过液体和蒸汽扩散进入1-3的空腔通道以及通过单晶到单晶的溶剂热客体交换嵌入到1-3的骨架中。在Al(OH)BDC和Ga(OH，F)BDC的情况下，观察到了两个不同取向的可相互转化的、依赖于客体浓度的吡啶客体相，而在Ga(OH)BDC中只有一个吡啶取向。
Single crystals of Ga(OH)(C(8)H(4)O(4)).0.74C(8)H(6)O(4) (2) and Ga(OH,F)(C(8)H(4)O(4)).0.74C(8)H(6)O(4) (3) were obtained under hydrothermal conditions. The structures of 2 and 3 have the same topological framework as the previously reported aluminum 1,4-benzenedicarboxylate (BDC), Al(OH)(C(8)H(4)O(4)).0.7C(8)H(6)O(4) (1). The frameworks are built by interconnecting M-OH-M chains (M = Al, Ga) with BDC anions to form large diamond-shaped one-dimensional channels filled with additional H(2)BDC guest molecules occupying disordered positions in the channels. Upon removal of H(2)BDC, other guest molecules such as H(2)O and pyridine can be inserted. In this work, we present a study of the intercalation of aromatic guests (BDC and pyridine) into frameworks of 1-3 by liquid and vapor diffusion into the empty channels of 1 and by single-crystal-to-single-crystal solvothermal guest exchange for 2 and 3. In the case of Al(OH)BDC and Ga(OH,F)BDC, two interconvertible, guest-concentration-dependent phases with different orientations of the pyridine guests have been observed, while only one pyridine orientation is found in Ga(OH)BDC.