{"title":"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。","authors":"Zhaohan Lu, Yabei Wu and Zhiyong Wang*, ","doi":"10.1021/acs.inorgchem.5c02678","DOIUrl":null,"url":null,"abstract":"<p >Endohedral metallofullerenes Ln<sub>2</sub>@C<sub>80</sub> (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 Gd<sub>2</sub>M@C<sub>80</sub>. Unlike previous approaches that rely on exohedral functionalization or cage modification, our method preserves the pristine <i>I</i><sub>h</sub>-C<sub>80</sub> 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 Gd<sub>2</sub>K@C<sub>80</sub> metallofullerene exhibits the largest reported coupling constant among metallofullerenes (+238 cm<sup>–1</sup>). 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 Ln<sub>2</sub>@C<sub>80</sub> systems while remarkably enhancing their intrinsic magnetic characteristics.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 29","pages":"15292–15300"},"PeriodicalIF":4.7000,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Theoretical Design of Mixed-Metal Endohedral Fullerenes Gd2M@C80 (M = Group IA or IIIA Metal) with Strong Intramolecular Magnetic Coupling\",\"authors\":\"Zhaohan Lu, Yabei Wu and Zhiyong Wang*, \",\"doi\":\"10.1021/acs.inorgchem.5c02678\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Endohedral metallofullerenes Ln<sub>2</sub>@C<sub>80</sub> (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 Gd<sub>2</sub>M@C<sub>80</sub>. Unlike previous approaches that rely on exohedral functionalization or cage modification, our method preserves the pristine <i>I</i><sub>h</sub>-C<sub>80</sub> 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 Gd<sub>2</sub>K@C<sub>80</sub> metallofullerene exhibits the largest reported coupling constant among metallofullerenes (+238 cm<sup>–1</sup>). 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 Ln<sub>2</sub>@C<sub>80</sub> systems while remarkably enhancing their intrinsic magnetic characteristics.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 29\",\"pages\":\"15292–15300\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-07-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02678\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02678","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
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.
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.