He Zheng, Gao En-Qing, Wang Zhe-Ming, Yan Chun-Hua, Kurmoo Mohamedally
State Key Lab of Rare Earth Materials Chemistry and Applications, Peking University, Beijing 100871,China.
Inorg Chem. 2005 Feb 21;44(4):862-74. doi: 10.1021/ic0487575.
Fourteen three-dimensional coordination polymers of general formula [Ln(lNO)(H2O)(SO4)]n, where Ln = La, 1.La; Ce, 2.Ce; Pr, 3.Pr; Nd, 4.Nd; Sm, 5.Sm; Eu, 6.Eu; Gd, 7.Gd; Tb, 8.Tb; Dy, 9.Dy; Ho, 10.Ho; Er. 11.Er; Tm, 12.Tm; Yb, 13.Yb; and Lu, 14.Lu; INO = isonicotinate-N-oxide, have been synthesized by hydrothermal reactions of Ln3+, MnCO3, MnSO4 x H2O, and isonicotinic acid N-oxide (HINO) at 155 degrees C and characterized by single-crystal X-ray diffraction, IR, thermal analysis, luminescence spectroscopy, and the magnetic measurement. The structures are formed by connection of layer, chain, or dimer of Ln-SO4 by the organic connector, INO. They belong to three structural types that are governed exclusively by the size of the ions: type I for the large ions, La, Ce, and Pr; type II for the medium ions, Nd, Sm, Eu, Gd, and Tb; and type III for the small ions, Dy, Ho, Er, Tm, Yb, and Lu. Type I consists of two-dimensional undulate Ln-sulfate layers pillared by INO to form a three-dimensional network. Type II has a 2-fold interpenetration of "3D herringbone" networks, in which the catenation is sustained by extensive pi-pi interactions and O-H...O and C-H...O hydrogen bonds. Type III comprises one-dimensional chains that are connected by INO bridges, resulting in an alpha-Po network. The progressive structural change is due to the metal coordination number decreasing from nine for the large ions via eight to seven for the small ions, demonstrating clearly the effect of lanthanide contraction. The sulfate ion acts as a micro4- or micro3-bridge, connecting two, three, or four metals, and is both mono- and bidentate. The INO ligand acts as a micro3- or micro2-bridge with carboxylate group in syn-syn bridging or bidentate chelating mode. The materials show considerably high thermal stability. The magnetic properties of 4.Nd, 6.Eu, 7.Gd, and 13.Yb and the luminescence properties of 6.Eu and 8.Tb are also investigated.
合成了14种通式为[Ln(lNO)(H₂O)(SO₄)]ₙ的三维配位聚合物，其中Ln = La（1.La）、Ce（2.Ce）、Pr（3.Pr）、Nd（4.Nd）、Sm（5.Sm）、Eu（6.Eu）、Gd（7.Gd）、Tb（8.Tb）、Dy（9.Dy）、Ho（10.Ho）、Er（11.Er）、Tm（12.Tm）、Yb（13.Yb）和Lu（14.Lu）；INO = 异烟酸 - N - 氧化物，通过Ln³⁺、MnCO₃、MnSO₄·H₂O和异烟酸N - 氧化物（HINO）在155℃下的水热反应合成，并通过单晶X射线衍射、红外光谱、热分析、发光光谱和磁性测量进行了表征。这些结构是由有机连接体INO连接Ln - SO₄的层、链或二聚体形成的。它们属于三种结构类型，完全由离子大小决定：大离子La、Ce和Pr为I型；中离子Nd、Sm、Eu、Gd和Tb为II型；小离子Dy、Ho、Er、Tm、Yb和Lu为III型。I型由二维起伏的Ln - 硫酸盐层组成，由INO支撑形成三维网络。II型具有“3D人字形”网络的2重互穿，其中的连锁通过广泛的π-π相互作用以及O - H...O和C - H...O氢键得以维持。III型由通过INO桥连接的一维链组成，形成α-Po网络。结构的逐步变化是由于金属配位数从大离子的9通过8减小到小离子的7，清楚地证明了镧系收缩的影响。硫酸根离子作为μ₄-或μ₃-桥，连接两个、三个或四个金属，并且既是单齿又是双齿的。INO配体以顺式 - 顺式桥连或双齿螯合模式作为μ₃-或μ₂-桥与羧酸根基团相连。这些材料表现出相当高的热稳定性。还研究了4.Nd、6.Eu、7.Gd和13.Yb的磁性以及6.Eu和8.Tb的发光性质。
