Alkaline earth metal mediated inter-molecular magnetism in perfluorocubane dimers and chains

Fuente: arXiv
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Autori principali: Li, Zhuohang, Wang, Cong, Zhou, Linwei, Guan, Yurou, Wu, Linlu, Dai, Jiaqi, Ji, Wei
Natura: Preprint
Pubblicazione: 2024
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author Li, Zhuohang
Wang, Cong
Zhou, Linwei
Guan, Yurou
Wu, Linlu
Dai, Jiaqi
Ji, Wei
author_facet Li, Zhuohang
Wang, Cong
Zhou, Linwei
Guan, Yurou
Wu, Linlu
Dai, Jiaqi
Ji, Wei
contents Perfluorocubane ($C_8F_8$) was successfully synthesized and found to accept and store electrons in its internal cubic cavity to form magnetic moments. However their inter-molecule spin-exchange coupling mechanism is yet to be revealed. In this study, we found the inter-molecule magnetic groundstates of $C_8F_8$ dimer and one-dimensional (1D) chain are tunable from antiferromagnetic (AFM) to ferromagnetic (FM) by stacking orders and alkaline earth metals intercalation using first-principle calculations. The inter-molecule couplings are dominated by noncovalent halogen $C-F...C_4$ interactions. Stacking orders of dimers can regulate the relative position of the lone pairs and $σ-holes$ at the molecular interface and thus the magnetic groundstates. Alkaline earth metals M (M = Na, Mg) intercalations could form $C_4-M-C_4$ bonds and lead to FM direct exchange at the inter-molecule region. An unpaired electron donated by the intercalated atoms or electron doping can result in a local magnetic moment in dimers, exhibiting an on-off switching by the odd-even number of electron filling. Novel electronic properties such as spin gapless semiconductor and charge density wave (CDW) states emerge when $C_8F_8$ molecules self-assemble with intercalated atoms to form 1D chains. These findings manifest the roles of stacking and intercalation in modifying intermolecular magnetism and the revealed halogen bond-dominated exchange mechanisms are paramount additions to those previously established non-covalent couplings.
format Preprint
id arxiv_https___arxiv_org_abs_2405_12060
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Alkaline earth metal mediated inter-molecular magnetism in perfluorocubane dimers and chains
Li, Zhuohang
Wang, Cong
Zhou, Linwei
Guan, Yurou
Wu, Linlu
Dai, Jiaqi
Ji, Wei
Materials Science
Mesoscale and Nanoscale Physics
Atomic and Molecular Clusters
Perfluorocubane ($C_8F_8$) was successfully synthesized and found to accept and store electrons in its internal cubic cavity to form magnetic moments. However their inter-molecule spin-exchange coupling mechanism is yet to be revealed. In this study, we found the inter-molecule magnetic groundstates of $C_8F_8$ dimer and one-dimensional (1D) chain are tunable from antiferromagnetic (AFM) to ferromagnetic (FM) by stacking orders and alkaline earth metals intercalation using first-principle calculations. The inter-molecule couplings are dominated by noncovalent halogen $C-F...C_4$ interactions. Stacking orders of dimers can regulate the relative position of the lone pairs and $σ-holes$ at the molecular interface and thus the magnetic groundstates. Alkaline earth metals M (M = Na, Mg) intercalations could form $C_4-M-C_4$ bonds and lead to FM direct exchange at the inter-molecule region. An unpaired electron donated by the intercalated atoms or electron doping can result in a local magnetic moment in dimers, exhibiting an on-off switching by the odd-even number of electron filling. Novel electronic properties such as spin gapless semiconductor and charge density wave (CDW) states emerge when $C_8F_8$ molecules self-assemble with intercalated atoms to form 1D chains. These findings manifest the roles of stacking and intercalation in modifying intermolecular magnetism and the revealed halogen bond-dominated exchange mechanisms are paramount additions to those previously established non-covalent couplings.
title Alkaline earth metal mediated inter-molecular magnetism in perfluorocubane dimers and chains
topic Materials Science
Mesoscale and Nanoscale Physics
Atomic and Molecular Clusters
url https://arxiv.org/abs/2405.12060