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Two novel coordination polymers in the family of lanthanide complexes with o-phenylenedioxydiacetato as ligand

机译:镧系配合物以邻苯二氧二乙酸为配体的两种新型配位聚合物

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摘要

Two novel coordination polymers [Ce(PDOA)(NO3)(H2O)2]n (1) and {[Ce(PDOA)(NO3)(H2O)3]·H2O}n (2) (PDOA = o-phenylenedioxydiacetato) have been prepared using hydrothermal conditions and have been structurally characterized. In both crystal structures 1 and 2 the Ce(III) atoms are decacoordinated by oxygen atoms from PDOA ligands with chelating and bridging functions, chelating nitrato ligands and aqua ligands. While in 1 the PDOA ligand presents a hexadentate coordination mode, in 2 it is coordinated in a pentadentate manner; this difference leads to different types of one-dimensional structural motifs: in 2 there are zig-zag chains of the -Ce-O-C-O-Ce- type with syn-anti carboxylate bridges and in 1 these chains are additionally interlinked by further syn-anti carboxylate bridges leading to a strip- or ribbon-like arrangement formed of {Ce3} fused triangles. The endothermic dehydration of 1 within the temperature range 69-199 °C is at least a two-step process as suggested by TG and DTA methods. A variable temperature (2-300 K) magnetic study reveals Curie-Weiss behavior for 1 with θ = -35.5 K observed above 50 K. The origin of the observed behavior is discussed.
机译:两种新型配位聚合物[Ce(PDOA)(NO3)(H2O)2] n(1)和{[Ce(PDOA)(NO3)(H2O)3]·H2O} n(2)(PDOA =邻苯二甲氧基二乙二酸酯)已经使用水热条件制备并且已经进行了结构表征。在晶体结构1和2中,Ce(III)原子都被来自具有螯合和桥连功能的PDOA配体,螯合硝酸根配体和水配体的氧原子分解。 PDOA配体在1中呈现六齿配位模式,而在2中则以五齿配位;这种差异会导致不同类型的一维结构基序:在2种中,-Ce-OCO-Ce-型之字形链具有顺-抗羧酸盐桥,在1中,这些链还通过进一步的顺-抗相互连接羧酸盐桥导致由{Ce3}融合三角形形成的条状或带状排列。如TG和DTA方法所建议,在69-199°C的温度范围内1的吸热脱水至少是两步过程。可变温度(2-300 K)磁性研究揭示了在50 K以上观察到的θ= -35.5 K时1的居里-魏斯行为。讨论了观察到的行为的起源。

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