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Synthesis and Magnetic Properties of Bis-Halobenzene Decamethyldysprosocenium Cations
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2024-02-21 , DOI: 10.1021/acs.inorgchem.3c04106 Sophie C Corner 1 , Gemma K Gransbury 1 , Iñigo J Vitorica-Yrezabal 1 , George F S Whitehead 1 , Nicholas F Chilton 1 , David P Mills 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2024-02-21 , DOI: 10.1021/acs.inorgchem.3c04106 Sophie C Corner 1 , Gemma K Gransbury 1 , Iñigo J Vitorica-Yrezabal 1 , George F S Whitehead 1 , Nicholas F Chilton 1 , David P Mills 1
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The decamethyldysprosocenium cation, [Dy(Cp*)2]+ (Cp* = {C5Me5}), was a target single-molecule magnet (SMM) prior to the isolation of larger dysprosocenium cations, which have recently shown magnetic memory effects up to 80 K. However, the relatively short Dy···Cp*centroid distances of [Dy(Cp*)2]+, together with the reduced resonance of its vibrational modes with electronic states compared to larger dysprosocenium cations, could lead to more favorable SMM behavior. Here, we report the synthesis and magnetic properties of a series of solvated adducts containing bis-halobenzene decamethyldysprosocenium cations, namely [Dy(Cp*)2(PhX-κ-X)2][Al{OC(CF3)3}4] (X = F or Cl) and [Dy(Cp*)2(C6H4F2-κ2-F,F)(C6H4F2-κ-F)][Al{OC(CF3)3}4]. These complexes were prepared by the sequential reaction of [Dy(Cp*)2(μ-BH4)]∞ with allylmagnesium chloride and [NEt3H][Al{OC(CF3)3}4], followed by recrystallization from parent halobenzenes. The complexes were characterized by powder and single crystal X-ray diffraction, NMR and ATR-IR spectroscopy, elemental analysis, and SQUID magnetometry; experimental data were rationalized by a combination of density functional theory and ab initio calculations. We find that bis-halobenzene adducts of the [Dy(Cp*)2]+ cation exhibit highly bent Cp*···Dy···Cp* angles; these cations are also susceptible to decomposition by C–X (X = F, Cl, Br) activation and displacement of halobenzenes by O-donor ligands. The effective energy barrier to reversal of magnetization measured for [Dy(Cp*)2(PhF-κ-F)2][Al{OC(CF3)3}4] (930(6) cm–1) sets a new record for SMMs containing {Dy(Cp*)2} fragments, though all SMM parameters are lower than would be predicted for an isolated [Dy(Cp*)2]+ cation, as expected due to transverse ligand fields introduced by halobenzenes and the large deviation of the Cp*···Dy···Cp* angle from linearity promoting magnetic relaxation.
中文翻译：
双卤代苯十甲基镝阳离子的合成及磁性
十甲基镝阳离子，[Dy(Cp*) 2 ] + (Cp* = {C 5 Me 5 })，是在分离较大的镝阳离子之前的目标单分子磁体 (SMM)，最近显示出磁记忆效应高达 80 K。然而，与较大的镝阳离子相比，[Dy(Cp*) 2 ] +的 Dy·Cp*质心距离相对较短，加上其振动模式与电子态的共振减少，可能会导致更有利的 SMM 行为。在这里，我们报道了一系列含有双卤代苯十甲基镝阳离子的溶剂化加合物的合成和磁性加合物，即[Dy(Cp*) 2 (PhX-κ- X ) 2 ][Al{OC(CF 3 ) 3 } 4 ] (X = F 或 Cl) 和 [Dy(Cp*) 2 (C 6 H 4 F 2 -κ 2 - F , F )(C 6 H 4 F 2 -κ- F )][Al{OC(CF 3 ) 3 } 4 ]。这些配合物是通过[Dy(Cp*) 2 (μ-BH 4 )] ∞与烯丙基氯化镁和[NEt 3 H][Al{OC(CF 3 ) 3 } 4 ]顺序反应，然后从母体卤代苯。通过粉末和单晶 X 射线衍射、NMR 和 ATR-IR 光谱、元素分析和 SQUID 磁力测定对配合物进行了表征；实验数据通过密度泛函理论和从头计算的结合合理化。 我们发现[Dy(Cp*) 2 ] +阳离子的双卤代苯加合物表现出高度弯曲的Cp*···Dy···Cp*角；这些阳离子也容易被 C–X (X = F、Cl、Br) 活化分解，并被 O-供体配体取代卤代苯。 [Dy(Cp*) 2 (PhF-κ- F ) 2 ][Al{OC(CF 3 ) 3 } 4 ] (930(6) cm –1 ) 测量的磁化反转的有效能垒设定了新的值包含 {Dy(Cp*) 2 } 片段的 SMM 的记录，尽管所有 SMM 参数都低于对分离的 [Dy(Cp*) 2 ] +阳离子的预测，正如预期的那样，这是由于卤代苯引入的横向配体场和Cp*…Dy…Cp* 角度与线性的大偏差促进磁弛豫。
更新日期：2024-02-21
中文翻译：
双卤代苯十甲基镝阳离子的合成及磁性
十甲基镝阳离子，[Dy(Cp*) 2 ] + (Cp* = {C 5 Me 5 })，是在分离较大的镝阳离子之前的目标单分子磁体 (SMM)，最近显示出磁记忆效应高达 80 K。然而，与较大的镝阳离子相比，[Dy(Cp*) 2 ] +的 Dy·Cp*质心距离相对较短，加上其振动模式与电子态的共振减少，可能会导致更有利的 SMM 行为。在这里，我们报道了一系列含有双卤代苯十甲基镝阳离子的溶剂化加合物的合成和磁性加合物，即[Dy(Cp*) 2 (PhX-κ- X ) 2 ][Al{OC(CF 3 ) 3 } 4 ] (X = F 或 Cl) 和 [Dy(Cp*) 2 (C 6 H 4 F 2 -κ 2 - F , F )(C 6 H 4 F 2 -κ- F )][Al{OC(CF 3 ) 3 } 4 ]。这些配合物是通过[Dy(Cp*) 2 (μ-BH 4 )] ∞与烯丙基氯化镁和[NEt 3 H][Al{OC(CF 3 ) 3 } 4 ]顺序反应，然后从母体卤代苯。通过粉末和单晶 X 射线衍射、NMR 和 ATR-IR 光谱、元素分析和 SQUID 磁力测定对配合物进行了表征；实验数据通过密度泛函理论和从头计算的结合合理化。 我们发现[Dy(Cp*) 2 ] +阳离子的双卤代苯加合物表现出高度弯曲的Cp*···Dy···Cp*角；这些阳离子也容易被 C–X (X = F、Cl、Br) 活化分解，并被 O-供体配体取代卤代苯。 [Dy(Cp*) 2 (PhF-κ- F ) 2 ][Al{OC(CF 3 ) 3 } 4 ] (930(6) cm –1 ) 测量的磁化反转的有效能垒设定了新的值包含 {Dy(Cp*) 2 } 片段的 SMM 的记录，尽管所有 SMM 参数都低于对分离的 [Dy(Cp*) 2 ] +阳离子的预测，正如预期的那样，这是由于卤代苯引入的横向配体场和Cp*…Dy…Cp* 角度与线性的大偏差促进磁弛豫。
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