Key Laboratory of Advanced Energy Materials Chemistry, Department of Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.
Laboratoire de Chimie de Coordination du CNRS (LCC-CNRS), Université de Toulouse, Centre National de la Recherche Scientifique (CNRS), 31077 Toulouse, France.
Molecules. 2023 Mar 9;28(6):2514. doi: 10.3390/molecules28062514.
Employing the new nitronyl nitroxide biradical ligand biNIT-3Py-5-Ph (2-(5-phenyl-3-pyridyl)-bis(4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide)), a 16-spin Cu-radical complex, [Cu(biNIT-3Py-5-Ph)(hfac)] , and three 2p-3d-4f chain complexes, {[Ln(hfac)]Cu(hfac)} (Ln= Gd , Tb , Dy ; hfac = hexafluoroacetylacetonate), have been prepared and characterized. X-ray crystallographic analysis revealed in all derivatives a common cyclic [Cu-biNIT] secondary building unit in which two bi-NIT-3Py-5-Ph biradical ligands and two Cu ions are associated via the pyridine N atoms and NO units. For complex , two such units assemble with four additional Cu ions to form a discrete complex involving 16 = 1/2 spin centers. For complexes -, the [Cu-biNIT] units are linked by Ln ions via NO groups in a 1D coordination polymer. Magnetic studies show that the coordination of the aminoxyl groups with Cu or Ln ions results in behaviors combining ferromagnetic and antiferromagnetic interactions. No slow magnetic relaxation behavior was observed for Tb and Dy derivatives.
采用新的硝酰氮自由基双自由基配体 biNIT-3Py-5-Ph（2-（5-苯基-3-吡啶基）-双（4,4,5,5-四甲基咪唑啉-1-氧-3-氧化物）），合成了一个 16 自旋 Cu-自由基配合物 [Cu（biNIT-3Py-5-Ph）（hfac）] 和三个 2p-3d-4f 链配合物，{[Ln（hfac）][Cu（hfac）]（biNIT-3Py-5-Ph）}（Ln=Gd，Tb，Dy；hfac=六氟乙酰丙酮酸盐），并对它们进行了表征。X 射线晶体学分析表明，在所有衍生物中，都存在一个常见的环状[Cu-biNIT]二级构建单元，其中两个双-NIT-3Py-5-Ph 双自由基配体和两个 Cu 离子通过吡啶 N 原子和 NO 单元连接。对于配合物，两个这样的单元与另外四个 Cu 离子组装，形成一个离散的复合物，其中包含 16 个 = 1/2 自旋中心。对于配合物-，[Cu-biNIT]单元通过 Ln 离子通过 NO 基团在一维配位聚合物中连接。磁性研究表明，氨基氧与 Cu 或 Ln 离子的配位导致了铁磁和反铁磁相互作用的组合。Tb 和 Dy 衍生物没有观察到缓慢的磁弛豫行为。
