Four novel compounds based on α-metatungstate [H2W12O40]6− (W12) and Ln-organic complexes, (NH4)4[Ln2(L)2(H2O)9(H2W12O40)]·nH2O (Ln=EuIII (1), GdIII (2), DyIII (4), n=11; TbIII (3), n=12; L=pyridine-3,5-dicarboxylate dianion) have been synthesized in aqueous solution and characterized by element analysis, IR spectrometry and thermogravimetric analysis. Single-crystal X-ray diffraction analyses reveal these compounds are isostructural with a P21/n space group. The W12 cluster acting as a tridentate ligand connects three Ln3+ ions, in turn, each Ln2 ion links two W12 clusters, as a result, a W12-Ln polymeric chain is formed. Coordination of pyridine-3,5-dicarboxylate ligands to the Ln3+ ions leads to a Ln-L polymeric chain. The two chains, W12-Ln and Ln-L, share Ln2 ions, resulting in a 2-D layer. Ring coordination of pyridine-3,5-dicarboxylate and W12 to the Ln ions changes some bond angles of W12 that leads to a slight distortion of W12 and splitting of vibration band of W-Oc-W. Solid-state photoluminescence properties of compounds 1−4 have been investigated. 相似文献
The macromolecular architecture is the crucial factor in determining the arrangement of the ordering structures, which, because of the multiscale feature, may exhibit distinct melting behaviors and induce the so-called memory effect to affect the following recrystallization. Until present, the correlation between the occurrence of memory effect and the intrinsic molecular structure is still far from the comprehensive understanding. In this work, four kinds of 1-butene/α-olefin random copolymers were designed and synthesized using the (pyridyl-amino) hafnium catalyst to introduce the different branches. The branch length was precisely controlled by the specific α-olefin comonomers, which include 1-hexene, 1-decene, 1-tetradecene, and 1-octadecene, while the branch density was tuned by the incorporation. As expected, the incorporation of α-olefin co-units to poly(1-butene) backbone decreases the non-isothermal crystallization kinetics and the degree of crystallinity. More interestingly, the resulting linear branch can induce the occurrence of memory effect and the threshold concentration of co-units (i.e., branch density) decreases with increasing the branch length. Based on the results of these 1-butene/α-olefin copolymers with designable branches, a direct correlation with the occurrence of memory effect and the fraction of amorphous region was established, which quantitatively indicates the degree of local segregation of the crystallized poly(1-butene) sequences by the α-olefin co-units.