具有强分子内磁耦合的混合金属内嵌富勒烯Gd2M@C80 (M = IA或IIIA族金属)的理论设计。

IF 4.7 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Zhaohan Lu, Yabei Wu and Zhiyong Wang*, 
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引用次数: 0

摘要

内嵌金属富勒烯Ln2@C80 (Ln =镧系元素)是一类令人着迷的分子磁体,由于其独特的单电子金属-金属键,它与被封装的镧系元素原子的4f电子强烈相互作用。然而,一个关键的限制来自于它们不稳定的三重态基态,这使得实验分离和实际应用变得复杂。为了解决这一挑战,我们提出了一种内嵌式掺杂策略,通过引入第三种金属原子(M = IA族或IIIA族金属)来形成混合金属富勒烯Gd2M@C80。与以往依赖于外面体功能化或笼型修饰的方法不同,我们的方法保留了原始的Ih-C80结构。我们的计算研究表明,这些金属富勒烯具有很强的分子内磁耦合,其耦合强度显示出基于离子半径m的可调性。值得注意的是,Gd2K@C80金属富勒烯在金属富勒烯中显示出最大的耦合常数(+238 cm-1)。详细的化学键分析揭示了不同的电子结构,这取决于掺杂剂:IA金属(Li, Na和K)在Gd-Gd- m簇上形成一个离域的三中心单电子(3c-1e)键,而IIIA金属(Al, Ga和In)表现出一个2c-1e的Gd-Gd键与一个涉及IIIA原子的3c-2e键共存。这项工作建立了一种创新的方法来稳定氧化还原活性Ln2@C80系统,同时显着增强其固有磁特性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Theoretical Design of Mixed-Metal Endohedral Fullerenes Gd2M@C80 (M = Group IA or IIIA Metal) with Strong Intramolecular Magnetic Coupling

Theoretical Design of Mixed-Metal Endohedral Fullerenes Gd2M@C80 (M = Group IA or IIIA Metal) with Strong Intramolecular Magnetic Coupling

Endohedral metallofullerenes Ln2@C80 (Ln = lanthanide) represent a fascinating class of molecular magnets due to their unique single-electron metal–metal bond, which strongly interacts with the 4f electrons of the encapsulated lanthanide atoms. However, a critical limitation arises from their unstable triplet ground state, which complicates experimental isolation and practical utilization. To address this challenge, we propose an endohedral doping strategy by introducing a third metal atom (M = group IA or IIIA metal) to form mixed-metal fullerenes Gd2M@C80. Unlike previous approaches that rely on exohedral functionalization or cage modification, our method preserves the pristine Ih-C80 structure. Our computational studies reveal strong intramolecular magnetic couplings in these metallofullerenes, with the coupling strength showing tunability based on the ionic radius of M. Notably, the Gd2K@C80 metallofullerene exhibits the largest reported coupling constant among metallofullerenes (+238 cm–1). A detailed bonding analysis uncovers distinct electronic structures, depending on the dopant: IA metals (Li, Na, and K) form a delocalized three-center-one-electron (3c-1e) bond across the Gd–Gd-M cluster, while IIIA metals (Al, Ga, and In) exhibit a 2c-1e Gd–Gd bond coexisting with a 3c-2e bond involving the IIIA atom. This work establishes an innovative approach to stabilize redox-active Ln2@C80 systems while remarkably enhancing their intrinsic magnetic characteristics.

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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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