Designed Syntheses of Three {Ni6PW9}-Based Polyoxometalates, from Isolated Cluster to Cluster-Organic Helical Chain

Three new hexa-Ni-substituted Keggin-type polyoxometalates (POMs), [Ni6(OH)3- (DACH)3(H2O)6(PW9O34)]·31H2O (1), [Ni(DACH)2][Ni6(OH)3(DACH)3(HMIP)2(H2O)2(PW9O34)]·56 H2O (2), and [Ni(DACH)2][Ni6(OH)3(DACH)2(AP)(H2O)5(PW9O34)]·2H2O (3) (DACH = 1,2-Diami- nocyclohexane, MIP = 5-Methylisophthalate, AP = Adipate) were successfully made in the presence of DACH under hydrothermal conditions. 1 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 1, 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 2 and the new 1D POM cluster organic chain (POMCOC) 3 were obtained. HMIP ligand still acts as a decorating group on the Ni6 core of 2 but results in the different spatial arrangement of the {Ni6PW9} units. AP ligands in 3 successfully bridge adjacent isolated POM cluster units to 1D POMCOC with left-hand helices. The AP in 3 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.