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具有氟化醇盐或芳氧基配体的基于铒的发光单分子磁体。

Luminescent Er based single molecule magnets with fluorinated alkoxide or aryloxide ligands.

作者信息

Selikhov Alexander N, Félix Gautier, Lyubov Dmitry M, Nelyubina Yulia V, Cherkasov Anton V, Sene Saad, Taydakov Ilya V, Metlin Mikhail T, Tyutyunov Andrey A, Guari Yannick, Larionova Joulia, Trifonov Alexander A

机构信息

A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 28 Vavilova str., 119334, Moscow, Russia.

Institute of Organometallic Chemistry of Russian Academy of Sciences, 49 Tropinina str., GSP-445, 630950, Nizhny Novgorod, Russia.

出版信息

Dalton Trans. 2024 Apr 2;53(14):6352-6366. doi: 10.1039/d3dt04375d.

Abstract

We report the synthesis, structures, and magnetic and luminescence properties of a series of new mono- and dinuclear Er complexes derived from sterically demanding aryloxide and fluorinated alkoxide ligands: [4-Bu-2,6-(PhCH)CHO]Er(THF) (1), [(CF)CO]Er(MeSiOH) (2), [(CF)CO]Er[(MeSi)NH] (3), [(CF)CO]Er(CHCH) (4), [(CF)CO]Er(-MeNCHCH) (5) and {[Ph(CF)CO]Er(μ-OC(CF)Ph)} (6). In compounds 1, 2, and 4, the Er ion is four-coordinated and adopts a distorted trigonal pyramidal geometry, while in 3, 5, and 6, the coordination geometry of Er is impacted by the presence of several relatively short Er⋯F distances, making them rather 6-coordinated. All compounds behave as field-induced Single Molecule Magnets (SMMs) and exhibit an Er characteristic near infrared (NIR) emission associated with the I → I transition with a remarkably long lifetime going up to 73 μs, which makes them multifunctional luminescent SMMs. The deconvolution of the NIR emission spectra allowed us to provide a direct probe of the crystal field splitting in these compounds, which was correlated with magnetic data.

摘要

我们报道了一系列由空间位阻较大的芳氧基和氟化醇盐配体衍生的新型单核和双核铒配合物的合成、结构以及磁学和发光性质:[4-Bu-2,6-(PhCH)CHO]Er(THF) (1)、[(CF)CO]Er(MeSiOH) (2)、[(CF)CO]Er[(MeSi)NH] (3)、[(CF)CO]Er(CHCH) (4)、[(CF)CO]Er(-MeNCHCH) (5) 和 {[Ph(CF)CO]Er(μ-OC(CF)Ph)} (6)。在化合物1、2和4中,铒离子为四配位,采用扭曲的三角锥几何构型,而在3、5和6中,铒的配位几何构型受到几个相对较短的Er⋯F距离的影响,使其呈现出六配位的状态。所有化合物均表现为场致单分子磁体 (SMMs),并表现出与I → I跃迁相关的铒特征近红外 (NIR) 发射,其寿命长达73 μs,这使它们成为多功能发光SMMs。近红外发射光谱的去卷积使我们能够直接探测这些化合物中的晶体场分裂,这与磁学数据相关。

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