College of Chemistry and Chemical Engineering, State Key Laboratory of Materials-oriented Chemical Engineering, Nanjing University of Technology, Nanjing 210009, PR China.
Dalton Trans. 2013 Jun 21;42(23):8454-9. doi: 10.1039/c3dt50155h. Epub 2013 Apr 26.
Two new inorganic-organic hybrid compounds Na2(C3N2H12)4{[Ni5(OH)3(H2O)4(CH3CO2)][Si2W18O66]}·12.5H2O (1) and (C3N2H12)3{[Co(II)2Co(III)4(OH)5(H2O)2(CH3CO2)][Si2W18O66]}·6H2O·(C3N2H10) (2), based on lacunary polyoxometalates and high-nuclear transition-metal clusters, have been synthesized by a new method (solvothermal method). Single crystal XRD, magnetic measurements, nonlinear-optical (NLO) measurements, thermogravimetric (TG) measurements, and IR spectra were performed to analyze the structures and properties of 1 and 2. XRD analyses reveal that compound 1 consists of an open Wells-Dawson anion Si2W18O66, a five-nuclear cationic cluster Ni5(OH)3(H2O)4(CH3CO2), free Na(+) cations, and protonated 1,3-diaminopropanes. Compound 2 has a similar structure to 1, while a six-nuclear cationic cluster Co(II)2Co(III)4(OH)5(H2O)2(CH3CO2) replaces the five-nuclear cationic cluster Ni5(OH)3(H2O)4(CH3CO2) in 1. Magnetic susceptibility measurements indicate antiferromagnetic interactions in 1, and the chirality of compound 2 may bring potential properties of catalysis and optical nonlinearity.
基于缺位多金属氧酸盐和多核过渡金属簇，通过一种新的方法（溶剂热法）合成了两个新的无机-有机杂化化合物 Na2(C3N2H12)4{[Ni5(OH)3(H2O)4(CH3CO2)][Si2W18O66]}·12.5H2O（1）和 (C3N2H12)3{[Co(II)2Co(III)4(OH)5(H2O)2(CH3CO2)][Si2W18O66]}·6H2O·(C3N2H10)（2）。单晶 XRD、磁性测量、非线性光学（NLO）测量、热重（TG）测量和红外光谱用于分析 1 和 2 的结构和性质。XRD 分析表明，化合物 1 由一个开放的 Wells-Dawson 阴离子Si2W18O66、一个五核阳离子簇Ni5(OH)3(H2O)4(CH3CO2)、游离的 Na(+)阳离子和质子化的 1,3-二氨基丙烷组成。化合物 2 具有与 1 相似的结构，而一个六核阳离子簇Co(II)2Co(III)4(OH)5(H2O)2(CH3CO2)取代了 1 中的五核阳离子簇Ni5(OH)3(H2O)4(CH3CO2)。磁性测量表明 1 中存在反铁磁相互作用，化合物 2 的手性可能带来潜在的催化和光学非线性性能。
