Reactivity differences of Sc3N@C2n (2n = 68 and 80). Synthesis of the first methanofullerene derivatives of Sc3N@D5h-C80

Cerón, Maira R.; Izquierdo, Marta; Alegret, Núria; Valdez, Juan A.; Rodríguez‐Fortea, Antonio; Olmstead, Marilyn M.; Balch, Alan L.; Poblet, Josep M.; Echegoyen, Luís

doi:10.1039/c5cc07416a

Cited by 64 publications

(16 citation statements)

References 42 publications

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“…In a related work, Echegoyen et al. reported the synthesis of five PCBM derivatives of Sc 3 N@ D 5 h ‐C 80 by reaction with the p ‐toluenesulfonyl (tosyl) hydrazone of phenyl butyric acid methyl ester, along with the X‐ray structure of one of the derivatives in which addition had occurred at the [6,6]‐(f−f) bond . Here, the regioselectivity in the photochemical reaction of Sc 3 N@ D 5 h ‐C 80 with 1 differs from that in the reaction with the hydrazone.…”

Section: Resultsmentioning

confidence: 98%

Adamantylidene Addition to M₃N@I_h‐C₈₀ (M=Sc, Lu) and Sc₃N@D_5h‐C₈₀: Synthesis and Crystallographic Characterization of the [5,6]‐Open and [6,6]‐Open Adducts

Yamada

Abe

Saito

et al. 2017

Chemistry A European J

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Additions of adamantylidene (Ad) to M N@I -C (M=Sc, Lu) and Sc N@D -C have been accomplished by photochemical reactions with 2-adamantyl-2,3'-[3H]-diazirine (1). In M N@I -C , the addition led to rupture of the [6,6]- or [5,6]-bonds of the I -C cage, forming the [6,6]-open fulleroid as the major isomer and the [5,6]-open fulleroid as the minor isomer. In Sc N@D -C , the addition also proceeded regioselectively to yield three major isomeric Ad mono-adducts, despite the fact that there are nine types of C-C bonds in the D -C cage. The molecular structures of the seven Ad mono-adducts, including the positions of the encaged trimetallic nitride clusters, have been unambiguously determined through single-crystal XRD analyses. Furthermore, results have shown that stepwise addition of Ad to Lu N@I -C affords several Ad bis-adducts, two of which have been isolated and characterized. The X-ray structure of one bis-adduct clearly revealed that the second Ad addition took place at a [6,6]-bond close to an endohedral metal atom. Theoretical calculations have also been performed to rationalize the regioselectivity.

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Section: Resultsmentioning

confidence: 98%

Adamantylidene Addition to M₃N@I_h‐C₈₀ (M=Sc, Lu) and Sc₃N@D_5h‐C₈₀: Synthesis and Crystallographic Characterization of the [5,6]‐Open and [6,6]‐Open Adducts

Yamada

Abe

Saito

et al. 2017

Chemistry A European J

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“…This incorporation of additional co‐ligand inside the cage is also likely to arrest the movement of the Co II ion inside the cage leading to less number of isomers and hence a robust SMMs. Experimentally several such fullerene cages are reported in the literature –…”

Section: Resultsmentioning

confidence: 99%

A Design Criteria to Achieve Giant Ising‐Type Anisotropy in Co^II‐Encapsulated Metallofullerenes

Singh

Shukla

Khatua

et al. 2019

Chemistry A European J

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Discovery of permanent magnetisation in molecules just like in hard magnets decades ago led to the proposal of utilising these molecules for information storage devices and also as Q‐bits in quantum computing. A significant breakthrough with a blocking temperature as high as 80 K has been recently reported for lanthanocene complexes. While enhancing the blocking temperature further remains one of the primary challenges, obtaining molecules that are suitable for the fabrication of the devices sets the bar very high in this area. Encouraged by the fact that our earlier predictions of potential single‐molecule magnets (SMMs) in lanthanide‐containing endohedral fullerenes have been verified, here we set out to undertake a comprehensive study on CoII‐ion‐encapsulated fullerene as potential SMMs. To study this class of molecules, we have utilised an array of theoretical methods ranging from density functional to ab initio CASSCF/NEVPT2 methods for obtaining reliable estimate of zero‐field splitting parameters D and E. Additionally, we have also employed, for the first time a combination of molecular dynamics based on DFT methods coupled with CASSCF/NEVPT2 methods to seek the role of conformational isomers in the relaxation of magnetisation. Particularly, we have studied, Co@C28, Co@C38 and Co@C48 cages and their isomers as potential target molecules that could yield substantial magnetic anisotropy. Our calculations categorically reveal a very large Ising anisotropy in this class of molecules, with Co@C48 cages predicted to yield D values as high as −127 cm−1. Our calculations on the smaller cages reveal the free movement of CoII ion inside the cage, leading to the likely scenario of faster relaxation of magnetisation. However, larger fullerene cages were found to solve this issue. Further models with incorporating units such as {CoOZn}, {CoScZnN} inside larger fullerenes yield axial zero‐field splitting values as high as −200 cm−1 with negligible E/D values. As these units represent a strong axiality coupled with a viable way to obtain air‐stable low‐coordinate CoII complexes, this opens up a new paradigm in the search of SMMs in this class of molecules.

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“…In 1999, with the great enthusiasm on EMFs, a brand‐new EMF, namely the cluster metallofullerene Sc 3 N@ I h ‐C 80 was discovered [20] . Up to now, a variety of metal clusters have been successfully encaged in fullerenes, such as mental nitrides, [21–23] sulfides, [24–26] carbides, oxides, [27–29] and even cyanides [30–32] . Specially, there is a controversy on the dimetallic fullerenes (di‐EMFs) M 2 C 2 n .…”

Section: Introductionmentioning

confidence: 99%

Stabilities, Geometries, Electronic Structures, and Conversion Rules of Carbide Cluster Metallofullerenes

Zhang

et al. 2022

The Chemical Record

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Since the discovery of the first carbide cluster metallofullerene (CCMF) Sc 2 C 2 @C 84 in 2001, CCMFs have attracted great concerns with variable structures and fascinating characteristics. To date, there are hundreds of studies on CCMFs. Crystallography studies on CCMFs are carried out by single-crystal X-ray diffraction. Theoretical calculations can also be used to study CCMFs in detail without being limited by low experimental yields. This review analyzes the stability of CCMFs reported previously, and indicates that the C 2 unit contributes a lot to their stability. At the same time, the relationship between the structures of inner carbide cluster and cage size is systematically discussed, and the four-electron transfer always occurs. Furthermore, the possible transformation rule between di-EMFs and CCMFs is indicated. Finally, an outlook regarding the future developments and applications of CCMFs is presented.

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Reactivity differences of Sc₃N@C_2n (2n = 68 and 80). Synthesis of the first methanofullerene derivatives of Sc₃N@D_5h-C₈₀

Cited by 64 publications

References 42 publications

Adamantylidene Addition to M₃N@I_h‐C₈₀ (M=Sc, Lu) and Sc₃N@D_5h‐C₈₀: Synthesis and Crystallographic Characterization of the [5,6]‐Open and [6,6]‐Open Adducts

Adamantylidene Addition to M₃N@I_h‐C₈₀ (M=Sc, Lu) and Sc₃N@D_5h‐C₈₀: Synthesis and Crystallographic Characterization of the [5,6]‐Open and [6,6]‐Open Adducts

A Design Criteria to Achieve Giant Ising‐Type Anisotropy in Co^II‐Encapsulated Metallofullerenes

Stabilities, Geometries, Electronic Structures, and Conversion Rules of Carbide Cluster Metallofullerenes

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Reactivity differences of Sc3N@C2n (2n = 68 and 80). Synthesis of the first methanofullerene derivatives of Sc3N@D5h-C80

Cited by 64 publications

References 42 publications

Adamantylidene Addition to M3N@Ih‐C80 (M=Sc, Lu) and Sc3N@D5h‐C80: Synthesis and Crystallographic Characterization of the [5,6]‐Open and [6,6]‐Open Adducts

Adamantylidene Addition to M3N@Ih‐C80 (M=Sc, Lu) and Sc3N@D5h‐C80: Synthesis and Crystallographic Characterization of the [5,6]‐Open and [6,6]‐Open Adducts

A Design Criteria to Achieve Giant Ising‐Type Anisotropy in CoII‐Encapsulated Metallofullerenes

Stabilities, Geometries, Electronic Structures, and Conversion Rules of Carbide Cluster Metallofullerenes

Contact Info

Product

Resources

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Reactivity differences of Sc₃N@C_2n (2n = 68 and 80). Synthesis of the first methanofullerene derivatives of Sc₃N@D_5h-C₈₀

Adamantylidene Addition to M₃N@I_h‐C₈₀ (M=Sc, Lu) and Sc₃N@D_5h‐C₈₀: Synthesis and Crystallographic Characterization of the [5,6]‐Open and [6,6]‐Open Adducts

Adamantylidene Addition to M₃N@I_h‐C₈₀ (M=Sc, Lu) and Sc₃N@D_5h‐C₈₀: Synthesis and Crystallographic Characterization of the [5,6]‐Open and [6,6]‐Open Adducts

A Design Criteria to Achieve Giant Ising‐Type Anisotropy in Co^II‐Encapsulated Metallofullerenes