Tubau Ànnia, Zinna Francesco, Di Bari Lorenzo, Font-Bardía Mercè, Vicente Ramon
Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Moruzzi 13, I 56124 Pisa, Italy.
Dalton Trans. 2024 Aug 13;53(32):13566-13582. doi: 10.1039/d4dt01295j.
The reaction of Ln(NO)·6HO (Ln = Nd, Sm, Eu, Tb, Dy, Tm and Yb) with the respective enantiopure ()-(-)-2-phenylbutyric or ()-(+)-2-phenylbutyric acid (/-2-HPhBut) and 4,7-diphenyl-1,10-phenanthroline (Bphen) allows the isolation of chiral dinuclear compounds of the formula [Ln(μ-/-2-PhBut)(/-2PhBut)(Bphen)] where Ln = Nd (R/S-Nd-a), Sm (R/S-Sm-a), Eu (R/S-Eu-a), Tb (R/S-Tb-a and R/S-Tb-b), Dy (R/S-Dy-a and R/S-Dy-b), Tm (R/S-Tm-b) and Yb (R/S-Yb-b). Single crystal X-ray diffraction was performed for compounds S-Eu-a and S-Tm-b. Powder crystal X-ray diffraction was performed for all complexes. From the crystallographic data two different structural motifs were found which are referred to as structure type and structure type . In structure type , the Ln atoms are bridged through four or -2-PhBut ligands with two different kinds of coordination modes whereas in structure type the two Ln atoms are bridged through four or -2-PhBut ligands showing only one kind of coordination mode. For those lanthanide ions exhibiting both structure types, Tb and Dy, a difference in the luminescence and magnetism behavior is observed. All compounds (except R/S-Tm-b) exhibit sensitized luminescence, notably the Eu and Tb analogues. Circular Dichroism (CD) and Circular Polarized Luminescence (CPL) in the solid state and in 1 mM dichloromethane (DCM) solutions are reported, leading to improved chiroptical properties for the DCM solutions. The asymmetry factor () in 1 mM DCM is ±0.02 (+ for R-Eu-a) for the magnetically allowed transition D → F and ±0.03 (+ for R-Tb-a and R-Tb-b) for the D → F transition. Magnetic properties of all compounds were studied and the Dy compound with the structural motif (R-Dy-b) shows Single Molecular Magnet (SMM) behavior under a 0 T magnetic field. However, R-Dy-a is a field-induced SMM.
Ln(NO)·6HO（Ln = Nd、Sm、Eu、Tb、Dy、Tm和Yb）与各自的对映体纯的（）-（-）-2-苯基丁酸或（）-（+）-2-苯基丁酸（/-2-HPhBut）以及4,7-二苯基-1,10-菲咯啉（Bphen）反应，可分离出式为[Ln(μ-/-2-PhBut)(/-2PhBut)(Bphen)]的手性双核化合物，其中Ln = Nd（R/S-Nd-a）、Sm（R/S-Sm-a）、Eu（R/S-Eu-a）、Tb（R/S-Tb-a和R/S-Tb-b）、Dy（R/S-Dy-a和R/S-Dy-b）、Tm（R/S-Tm-b）和Yb（R/S-Yb-b）。对化合物S-Eu-a和S-Tm-b进行了单晶X射线衍射。对所有配合物进行了粉末晶体X射线衍射。从晶体学数据中发现了两种不同的结构 motif，分别称为结构类型 和结构类型 。在结构类型 中，Ln原子通过四个 或 -2-PhBut配体以两种不同的配位模式桥连，而在结构类型 中，两个Ln原子通过四个 或 -2-PhBut配体桥连，仅显示一种配位模式。对于同时呈现两种结构类型的镧系离子Tb和Dy，观察到发光和磁性行为存在差异。所有化合物（除R/S-Tm-b外）均表现出敏化发光，尤其是Eu和Tb类似物。报道了固态和1 mM二氯甲烷（DCM）溶液中的圆二色性（CD）和圆偏振发光（CPL），从而改善了DCM溶液的手性光学性质。在1 mM DCM中，磁允许跃迁D → F的不对称因子（）为±0.02（R-Eu-a为 +），D → F跃迁的不对称因子为±0.03（R-Tb-a和R-Tb-b为 +）。研究了所有化合物的磁性，具有结构 motif （R-Dy-b）的Dy化合物在0 T磁场下表现出单分子磁体（SMM）行为。然而，R-Dy-a是场诱导的SMM。
