First-Principles Design of Low-Dimensional Organometallic Magnets with Novel Functions★

doi:10.6023/A25050144

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (9): 1035-1045.DOI: 10.6023/A25050144 Previous Articles Next Articles

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新型功能性低维金属有机磁体的第一性原理设计^★

吕海峰^a, 李星星^a^,^b^,^*()

^a 中国科学技术大学精准智能化学全国重点实验室合肥 230026
^b 中国科学技术大学化学物理系合肥 230026

投稿日期:2025-05-07 发布日期:2025-07-14

作者简介:

吕海峰, 中国科学技术大学副研究员. 2019年获中国科学技术大学博士学位. 研究方向为理论与计算化学, 主要从事低维功能材料理论设计与模拟, 近五年来在Nat. Phys.、Nat. Chem.、J. Am. Chem. Soc.、PRL等SCI期刊发表第一/通讯(含共同)作者论文40余篇.

李星星, 中国科学技术大学特任教授. 2015年于中国科学技术大学获博士学位. 2023年获基金委优秀青年基金资助. 长期致力于低维自旋材料和分子器件的第一性原理研究. 迄今为止在Nature Nanotech.、Nat. Commun.、Sci. Adv.、JACS、Angew、PRL等SCI期刊发表第一/通讯(含共同)作者论文60余篇. 曾获中国化学会青年化学奖、中国科学院院长特别奖等奖励.

^★ “中国青年化学家”专辑.

基金资助:
国家自然科学基金(22303092); 国家自然科学基金(22273092); 国家自然科学基金(22322304)

First-Principles Design of Low-Dimensional Organometallic Magnets with Novel Functions^★

Haifeng Lv^a, Xingxing Li^a^,^b^,^*()

^a State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026
^b Department of Chemical Physics, University of Science and Technology of China, Hefei 230026

Received:2025-05-07 Published:2025-07-14
Contact: * E-mail: lixx@ustc.edu.cn
About author:
^★ For the VSI “Rising Stars in Chemistry”.
Supported by:
National Natural Science Foundation of China(22303092); National Natural Science Foundation of China(22273092); National Natural Science Foundation of China(22322304)

Low-dimensional magnetic materials, which can simultaneously utilize the electrons’ spin and charge degrees of freedom for data storage, processing and transmission, exhibit significant potentials for applications in next-generation information technologies. However, the development of low-dimensional magnetic materials faces severe challenges such as the difficulties of experimental synthesis and characterization, usually low Curie temperatures, lack of effective modulation, and limited function integration. First-principles design of novel low-dimensional functional magnetic materials has thus emerged as a crucial approach to addressing these issues. In this context, organometallic systems have garnered widespread attentions due to their rich chemical tunability. Their diverse transition metal centers and extensive organic ligand libraries provide a vast design space for low-dimensional magnetic materials. The precisely controllable coordination environment can effectively modulate the charge and spin states of metal/ligand centers. Moreover, the coordination bonds between metals and ligands exhibit diverse and adjustable orbital coupling, offering an ideal platform for achieving high Curie temperatures and varied magnetic interactions. Additionally, the chemical modifiability and conformational flexibility of organic ligands facilitate the construction of magnetic phase-transition systems and multifunctional spintronic devices. This review aims to systematically summarize recent advances in the first-principles design of low-dimensional magnetic organometallic materials with targeted functions. Several key design strategies are highlighted, including methods for constructing stable magnets with long-range room-temperature ferrimagnetism, chemical modulation strategies for magnetic phase transitions, approaches to designing room-temperature multiferroic materials, principles for creating metal-organic materials with giant Rashba effects, design rules for bipolar magnetic molecules, inverse design of altermagnetic metal-organic frameworks (MOFs), and microscopic mechanisms of electric-field-controlled magnetism. Finally, the integration of machine learning methods to achieve low-dimensional metal-organic magnets with high magnetic anisotropy is discussed. By systematically outlining the unique advantages and existing challenges of organometallic systems in the design of low-dimensional magnetic materials, along with the latest experimental breakthroughs, this review is expected to provide theoretical guidance and technical pathways for future related researches.

Key words: first-principles design, room-temperature magnetism, low-dimensional organometallics, d-p direct interaction, room-temperature multiferroicity, bipolar magnetic molecule, altermagnetism

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Haifeng Lv, Xingxing Li. First-Principles Design of Low-Dimensional Organometallic Magnets with Novel Functions^★[J]. Acta Chimica Sinica, 2025, 83(9): 1035-1045.

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Fig. & Tab. 9

Figure 1. Schematic illustration of the transition from traditional d-p-d superexchange interaction to d-p direct exchange interaction. Metal and organic linkers are denoted by the green square and gray diamond[12]

Figure 2. (a) Realizing two-dimensional magnetic semiconductors with enhanced curie temperature by antiaromatic ring based organometallic frameworks[16]. (b) Two-dimensional bipolar magnetic semiconductors with high Curie-temperature and electrically controllable spin polarization realized in exfoliated Cr(pyrazine)2 monolayers[17]

Figure 3. (a) Enhanced Curie temperature of two-dimensional Cr(II) aromatic heterocyclic metal-organic framework magnets via strengthened orbital hybridization[21]. (b) Enhancing magnetic ordering in two-dimensional metal-organic frameworks via frontier molecular orbital engineering[22]

Figure 4. (a) Chemically controlled reversible magnetic phase transition in two-dimensional organometallic lattices[24]. (b) Tautomerization makes topological phase transition in 2D organometallic lattices[25]

Figure 5. (a) Two-Dimensional organic-inorganic room-temperature multiferroics[26]. (b) Quintuple function integration in two-dimensional Cr(II) five-membered heterocyclic metal organic frameworks via tuning ligand spin and lattice symmetry[27]. (c) A route to two-dimensional room-temperature organometallic multiferroics: the marriage of d-p spin coupling and structural inversion symmetry breaking[28]

Figure 6. Design of Rashba semiconductors in two-dimensional chiral metal-organic frameworks[29]

Figure 7. Bipolar magnetic molecules for control of spin-polarized electric current in molecular junctions[5d]

Figure 8. (a) Realizing altermagnetism in two-dimensional metal-organic framework semiconductors with electric-field-controlled anisotropic spin current[30]. (b) Inverse design of 2D altermagnetic metal-organic framework monolayers from Hückel theory of nonbonding molecular orbitals[31]

Figure 9. (a) Charting regions of cobalt’s chemical space with maximally large magnetic anisotropy: a computational high-throughput study[33]. (b) Transition-metal interlink neural network: machine learning of 2D metal-organic frameworks with high magnetic anisotropy[34]

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新型功能性低维金属有机磁体的第一性原理设计^★

First-Principles Design of Low-Dimensional Organometallic Magnets with Novel Functions^★

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新型功能性低维金属有机磁体的第一性原理设计★

First-Principles Design of Low-Dimensional Organometallic Magnets with Novel Functions★

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Fig. & Tab. 9

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新型功能性低维金属有机磁体的第一性原理设计^★

First-Principles Design of Low-Dimensional Organometallic Magnets with Novel Functions^★