MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China.
Molecules. 2022 Jul 4;27(13):4295. doi: 10.3390/molecules27134295.
Three new hexa-Ni-substituted Keggin-type polyoxometalates (POMs), [Ni(OH)- (DACH)(HO)(PWO)]·31HO (), [Ni(DACH)][Ni(OH)(DACH)(HMIP)(HO)(PWO)]·56 HO (), and [Ni(DACH)][Ni(OH)(DACH)(AP)(HO)(PWO)]·2HO () (DACH = 1,2-Diami- nocyclohexane, MIP = 5-Methylisophthalate, AP = Adipate) were successfully made in the presence of DACH under hydrothermal conditions. is an isolated hexa-Ni-substituted Keggin unit decorated by DACH. In order to further construct POM cluster-organic frameworks (POMCOFs) on the basis of , by analyzing the steric hindrances and orientations of the POM units, the rigid HMIP and flexible AP ligands were successively incorporated, and another anionic monomeric POM and the new 1D POM cluster organic chain (POMCOC) were obtained. HMIP ligand still acts as a decorating group on the Ni core of but results in the different spatial arrangement of the {NiPW} units. AP ligands in successfully bridge adjacent isolated POM cluster units to 1D POMCOC with left-hand helices. The AP in is the longest aliphatic carboxylic acid ligand in POMs, and the 1D POM cluster-AP helical chain represents the first 1D POMCOC with a helical feature.
三种新的六镍取代 Keggin 型多金属氧酸盐（POM），[Ni(OH)- (DACH)(HO)(PWO)]·31HO (1)，[Ni(DACH)][Ni(OH)(DACH)(HMIP)(HO)(PWO)]·56 HO (2)，和[Ni(DACH)][Ni(OH)(DACH)(AP)(HO)(PWO)]·2HO () (DACH = 1,2-二氨基环己烷，MIP = 5-甲基间苯二甲酸，AP = 己二酸)，在水热条件下，成功地在 DACH 的存在下制备。1 是一个被 DACH 修饰的孤立的六镍取代 Keggin 单元。为了在 1 的基础上进一步构建多金属氧酸盐簇-有机骨架（POMCOFs），通过分析 POM 单元的空间位阻和取向，成功地引入了刚性的 HMIP 和柔性的 AP 配体，并得到了另一个阴离子单体 POM 和新的 1D POM 簇有机链。HMIP 配体仍然作为 1 的 Ni 核上的装饰基团，但导致了{NiPW}单元的不同空间排列。AP 配体在 2 中成功地将相邻的孤立 POM 簇单元桥接到 1D POMCOC 上，形成左旋螺旋。2 中的 AP 是 POMs 中最长的脂肪族羧酸配体，1D POM 簇-AP 螺旋链代表了第一个具有螺旋特征的 1D POMCOC。
