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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Slow magnetic relaxation and luminescence properties in lanthanide(iii)/anil complexes
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Slow magnetic relaxation and luminescence properties in lanthanide(iii)/anil complexes

机译：镧系元素（III）/ anil络合物中的缓慢磁性松弛和发光性质

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摘要

The initial use of anils, i.e. bidentate Schiff bases derived from the condensation of anilines with salicylaldehyde or its derivatives, in 4f-metal chemistry is described. The 1?:?1 reactions between Ln(NO _(3) ) _(3) · x H _(2) O (Ln = lanthanide) or Y(NO _(3) ) _(3) ·6H _(2) O and N -(5-bromosalicylidene)aniline (5BrsalanH) in MeCN has provided access to complexes [Ln(NO _(3) ) _(3) (5BrsalanH) _(2) (H _(2) O)]·MeCN (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) and [Y(NO _(3) ) _(3) (5BrsalanH) _(2) (H _(2) O)]·MeCN, respectively, in good yields. The structures of the isomorphous complexes with Ln = Pr( 1 ·MeCN), Sm( 3 ·MeCN), Gd( 5 ·MeCN), Dy( 7 ·MeCN) and Er( 9 ·MeCN) have been determined by single-crystal X-ray crystallography. The other complexes were proven to be isostructural with the fully structurally characterized compounds based on elemental analyses, IR spectra, unit cell determinations and powder X-ray patterns. The 9-coordinate Ln ~(III) centre in the [Ln(NO _(3) ) _(3) (5BrsalanH) _(2) (H _(2) O)] molecules is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms that belong to the organic ligands and one oxygen atom from the aquo ligand. The 5BrsalanH molecules behave as monodentate O-donors; the acidic H atom is clearly located on the imino N atom and thus the formally neutral ligands adopt an extremely rare coordination mode participating in the zwitterionic form. The coordination polyhedra defined by the nine donor atoms around the Ln ~(III) centres are best described as spherical capped square antiprisms. Various intermolecular interactions build the crystal structures and Hirshfeld surface analysis was applied to evaluate the magnitude of interactions between the molecules. Solid-state IR and UV/VIS data are discussed in terms of structural features. ~(1) H NMR data prove that the diamagnetic [Y(NO _(3) ) _(3) (5BrsalanH) _(2) (H _(2) O)] complex decomposes in DMSO. Combined dc and ac magnetic susceptibility, as well as magnetization data for 7 suggest that this complex shows field-induced slow magnetic relaxation. Two magnetization relaxation processes are evident. The fit to the Arrhenius law has been performed using the 6.5–8.5 K ac data, affording an effective barrier for the magnetization reversal of 27 cm ~(?1) . Cole–Cole plot analysis in the temperature range in which the Orbach relaxation process is assumed, reveals a narrow distribution of relaxation times. The solid Dy( III ) complex 7 emits green light at 338 nm, the emission being ligand-centered. The perspectives of the present, first results in the lanthanide( III )-anil chemistry are critically discussed.
机译：描述了初始用途，即，在4F-金属化学中，描述了衍生自苯胺酰胺或其衍生物的苯胺缩合的二齿Schiff碱。 1？：α：1在LN之间的反应（NO _（3））_（3）·x H _（2）O（ln =镧）或y（no _（3））_（3）·6h _（ 2）O和N - （5-溴代基三烷基）苯胺（5brsalanh）在Mecn中提供了对复合物的进入[Ln（No _（3））_（3）（5BrsalanH）_（2）（H _（2）O） ]·mecn（ln = pr，nd，sm，eu，gd，tb，dy，ho，er，Yb）和[Y（no _（3））_（3）（5brsalanh）_（2）（h _ （2）o）]·MECN分别以良好的产量。用LN = Pr（1·MECN），SM（3·MECN），GD（5·MECN），DY（7·MECN）和ER（9·MECN）的结构的结构已经通过单晶确定X射线晶体学。被证明，基于元素分析，IR光谱，单位细胞测定和粉末X射线图案的完全结构表征化合物被证明是具有完全结构表征化合物的表人组织。 [LN（NO _（3））_（3）（5BrsalanH）（5brsalanH）（2）（H _（2）O）]分子中的9坐标Ln〜（III）中心与六个氧原子结合在一起三个二齿螯合硝酸盐组，属于有机配体的两个氧原子和来自Aquo配体的一个氧原子。 5brsalanh分子表现为单常图o捐助者;酸性H原子明显位于亚氨基N原子上，因此纯度中性配体采用参与两性离子形式的极少数配位模式。由LN〜（III）中心周围的九个供体原子定义的协调多面体最佳地描述为球形封端的方抗侵犯。各种分子间相互作用构建晶体结构和HIRSHFELD表面分析以评估分子之间的相互作用的大小。在结构特征方面讨论了固态IR和UV / VIS数据。 〜（1）H NMR数据证明了抗磁[Y（NO _（3））_（3）（5BrsalanH）_（2）（H _（2）O）]复杂在DMSO中分解。组合DC和AC磁化率，以及7的磁化数据表明，这种复合物显示出现场引起的缓慢磁性松弛。两种磁化放松过程很明显。已经使用6.5-8.5克AC数据进行了对Arrhenius法律进行的，为27cm〜（？1）的磁化反转提供有效屏障。在假设orbach弛豫过程的温度范围内COLE-COLE绘图分析，揭示了松弛时间的狭窄分布。固体Dy（III）复合物7在338nm处发射绿光，排放是以配体为中心的。本发明的前景，首先在镧系里（III） - anil化学的结果是批判性的。

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