Covalent interactions depend on the distances between metals and fullerenes for thermodynamically stable M@C78 (M = La, Ce, and Sm),Inorganic Chemistry Frontiers

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Covalent interactions depend on the distances between metals and fullerenes for thermodynamically stable M@C78 (M = La, Ce, and Sm)
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2020-05-29 , DOI: 10.1039/d0qi00428f
Mengyang Li _{1,

2,

3,

4,

5} , Yaoxiao Zhao _{1,

2,

3,

4,

5} , Yanbo Han _{1,

2,

3,

4,

5} , Kun Yuan _{6,

7,

8,

9} , Kaini Zhang _{1,

2,

3,

4,

5} , Yingqi Chen _{1,

2,

3,

4,

5} , Masahiro Ehara _{10,

11,

12} , Shigeru Nagase _{12,

13,

14,

15} , Xiang Zhao _{1,

2,

3,

4,

5}

Affiliation

Institute for Chemical Physics & Department of Chemistry
School of Science
State Key Laboratory of Electrical Insulation and Power Equipment & MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter
Xi'an Jiaotong University
Xi'an 710049
College of Chemical Engineering and Technology
Tianshui Normal University
Tianshui
China
Institute for Molecular Science
Okazaki
Japan
Fukui Institute for Fundamental Chemistry
Kyoto University
Kyoto 606-8103

Thermodynamically stable La@C_2v(24 107)-C₇₈, La@D_3h(24 109)-C₇₈, La@C₁(22 595)-C₇₈, Ce@D_3h(24 109)-C₇₈, Sm@C_2v(24 107)-C₇₈, and Sm@D_3h(24 109)-C₇₈ based on density functional theory and statistical thermodynamic analysis are studied in theory. C₁(22 595)-C₇₈, violating the isolated pentagon rule, is a second novel isomer stabilized by encaging a La atom. In addition, three- and two-electron transfers occur in M@C₇₈ (M = La and Ce) and Sm@C₇₈, respectively. Although there are two electrons transferred from Sm to C₇₈, these electrons transferred to the surface of C_2v(24 107)-C₇₈ are unpaired. Thus, the surface of the endohedral metallofullerene, Sm@C_2v(24 107)-C₇₈, firstly displays diradical characteristics. Notably, the spin states of the two electrons transferred from Sm to D_3h(24 109)-C₇₈ are different from those on C_2v(24 107)-C₇₈, leading to different spin ground states. Furthermore, the natural bond orders and bond critical point analyses on thermodynamically stable M@C₇₈ (M = La, Ce, and Sm) reveal that the distance between the metal and carbon atom plays an important role in the covalent interaction between the inner metal atoms and C₇₈. Because of the strong ionic interaction, the studies on the magnetic character of M@C₇₈ (M = La, Ce, and Sm) show that Sm@C₇₈ is a promising candidate for single-molecule magnets with high isotropic susceptibility. The infrared spectra were simulated to facilitate further experimental study on the stable M@C₇₈ (M = La, Ce, and Sm). We believe that this work will provide good guidance and assistance for the further study of mono-metallofullerenes and coordination compounds in both experiment and theory.

中文翻译：

共价相互作用取决于金属与富勒烯之间的距离，以实现热力学稳定的M @ C78（M = La，Ce和Sm）

热力学稳定的La @ C _2v（24 107）-C ₇₈，La @ D _3h（24 109）-C ₇₈，La @ C ₁（22 595）-C ₇₈，Ce @ D _3h（24 109）-C ₇₈，理论上研究了基于密度泛函理论和统计热力学分析的Sm @ C _2v（24107）-C ₇₈和Sm @ D _3h（24109）-C ₇₈。C ₁（22595）-C ₇₈违反孤立的五边形规则的是通过引入La原子而稳定的第二种新型异构体。另外，三电子和二电子转移分别发生在M @ C ₇₈（M = La和Ce）和Sm @ C _78中。尽管有两个电子从Sm转移到C ₇₈，但是这些转移到C _2v（24 107）-C ₇₈表面的电子是不成对的。因此，内面金属富勒烯Sm @ C _2v（24107）-C _78的表面首先显示双自由基特性。值得注意的是，两个电子的自旋态从钐转移到d _3小时（24 109）-C ₇₈是从那些在不同的C _2v（24 107）-C ₇₈，导致不同的自旋基态。此外，对热力学稳定的M @ C ₇₈（M = La，Ce和Sm）的自然键序和键临界点分析表明，金属与碳原子之间的距离在内部金属之间的共价相互作用中起着重要作用原子和C ₇₈。由于强的离子相互作用，对M @ C ₇₈（M = La，Ce和Sm）磁性的研究表明，Sm @ C ₇₈是具有高各向同性磁化率的单分子磁体的有希望的候选者。模拟了红外光谱，以便于在稳定的M @ C ₇₈上进行进一步的实验研究（M = La，Ce和Sm）。我们相信这项工作将为进一步研究单金属富勒烯和配位化合物的实验和理论提供良好的指导和协助。

更新日期：2020-06-30

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