‘Kick-in the head’: high-performance and air-stable mononuclear DyIII single-molecule magnets with pseudo-D6h symmetry from a [1 + 1] Schiff-base macrocycle approach†

IF 6.1 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Alexandros S. Armenis, Arpan Mondal, Sean R. Giblin, Dimitris I. Alexandropoulos, Jinkui Tang, Richard A. Layfield and Theocharis C. Stamatatos
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Abstract

Using the [1 + 1] condensation approach for the preparation of new macrocyclic scaffolds (LN6phen and LN4O2phen) with the rigid phenanthroline-based ‘head’ unit produces the air-stable mononuclear compounds [Dy(LN6phen)(Ph3SiO)2](PF6) (1-LN6phen) and [Dy(LN4O2phen)(Ph3SiO)2](PF6) (1-LN4O2phen) through a stepwise metal-ion templated synthesis. Both compounds exhibit pseudo-D6h symmetry with different degrees of distortion from the ideal hexagonal bipyramidal geometry, depending on the planarity of the equatorial macrocycles and the intramolecular π–π stacking interactions between the phenyl groups of the apical siloxide ligand and the equatorial macrocycle. Both compounds are single-molecule magnets (SMMs) with large energy barriers for the magnetization reversal, exhibiting out-of-phase AC susceptibility signals up to 75 K or 90 K. The closer-to-ideal D6h complex 1-LN4O2phen possesses a Ueff of 1360 K, which is the highest reported barrier among all mononuclear DyIII SMMs synthesized using the [1 + 1] Schiff-base macrocycle approach. The experimental results are supported by ab initio calculations, which indicate relaxation of the magnetization via the first- or second-excited state for 1-LN6phen and 1-LN4O2phen, respectively. The results demonstrate the ability of Schiff-base macrocycles to facilitate the synthesis of high-performance and air-stable SMMs through a chemical modulation of the individual carbonyl ‘head’ and amine subunits, deciphering the factors which affect the magnetic dynamics of SMMs.

Abstract Image

“踢头”:高性能和空气稳定的单核DyIII单分子磁体与伪d6h对称从[1+1]希夫碱大环方法†
采用[1+1]缩合法制备新型大环支架(“L”_“phen”^“N6”和“L”_“phen”^“N4O2”),以刚性菲罗啉为“头”单元,通过逐步金属离子模板法合成了空气稳定的单核化合物[Dy(“L”_“phen”^“N6”)(Ph3SiO)2](PF6)(1-“L”_“phen”^“N6”)和[Dy(“L”_“phen”^“N4O2”)(Ph3SiO)2](PF6)(1-“L”_“phen”^“N4O2”)。这两种化合物都表现出伪d6h对称,与理想的六方双锥体几何形状有不同程度的畸变,这取决于赤道大环的平面度以及顶端氧化硅配体的苯基与赤道大环之间的分子内π-π堆积相互作用。这两种化合物都是单分子磁体(SMMs),具有较大的磁化反转能量垒,在75 K或90 K时表现出异相交流磁化率信号。接近理想的D6h配合物1-“L”_“phen”^“N4O2”具有1360 K的Ueff,这是所有使用[1+1]希夫碱大环法合成的单核DyIII SMMs中报道的最高的势垒。实验结果得到了从头计算的支持,表明1- L - phen ^ N6和1- L - phen ^ N4O2分别通过第一激发态和第二激发态存在磁化弛豫。综合结果表明,希夫碱大环通过对单个羰基“头”和胺亚基的化学调制,促进了高性能和空气稳定的smm的合成,从而解释了影响smm磁动力学的因素。
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来源期刊
Inorganic Chemistry Frontiers
Inorganic Chemistry Frontiers CHEMISTRY, INORGANIC & NUCLEAR-
CiteScore
10.40
自引率
7.10%
发文量
587
审稿时长
1.2 months
期刊介绍: The international, high quality journal for interdisciplinary research between inorganic chemistry and related subjects
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