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Endo/On-Cage Boron Doping for Stabilization and Strong Magnetic Coupling in Metallofullerenes Gd2@C80 and Gd3@C80
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王
DOI：10.1021/acs.inorgchem.6c01663.png)
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Abstract
En 中文
Endohedral metallofullerenes Gd2@C80 and Gd3@C80 are typical redox-active gadolinium-based metallofullerenes with potential applications in molecular magnetic materials. However, their neutral forms suffer from intrinsic instability, which severely limits further applications. Herein, we perform systematic theoretical investigations to explore the regulating effects of endohedral and on-cage boron doping on the stability and magnetic properties of Gd2@C80 and Gd3@C80 and on the uncommon B(I) in Gd2B@C80. For dimetallofullerene Gd2@C80, it is discovered that endohedral doping leads to a boron atom that exists in an unusual +1 oxidation state, which has a similar electronic structure to monovalent borylenes. Broken-symmetry density functional theory (BS-DFT) calculations reveal a large magnetic coupling constant of J = 191 cm–1 for Gd2B@C80. For trimetallofullerene Gd3@C80, on-cage boron doping achieves dual effects of stabilization and magnetic induction. Single boron atom substitution eliminates the odd electron distribution on the carbon cage and doubles the HOMO–LUMO gap, while double boron atom substitution triggers the formation of a 3c-1e bond, rarely observed in metallofullerenes. A magnetic coupling constant of J = 146 cm–1 is induced in Gd3@C78B2 as calculated by BS-DFT. Our findings demonstrate that endo/on-cage boron doping is an effective strategy to stabilize redox-active Gd-based metallofullerenes and engineer strong magnetic coupling. The discovery of the 3c-1e bond in trimetallofullerenes opens up new possibilities for the design and construction of diverse high-performance molecular magnetic materials.
Keywords:
Boron
Doping
Magnetic properties
Molecular properties
Quantum mechanics
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4.7
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10.5W
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