Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C<sub>60</sub> Derivative

Hasegawa, Shota; Hashikawa, Yoshifumi; Kato, Tatsuhisa; Murata, Yasujiro

doi:10.1002/anie.201807823

Cited by 30 publications

(41 citation statements)

References 47 publications

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“…In the present case of encapsulated NO radical it was concluded from the broad variance of its principal g matrix values (Hasegawa et al, 2018a) that even at low temperatures the radical is not fixed to a particular site. It was remarkable that the very small value quoted for the axial component (Hasegawa et al, 2018a) of 1 https://doi.org/10.5194/mr-2020-11…”

Section: Introductionmentioning

confidence: 60%

“…In case of La@C 82 for instance it was possible to conclude from an analysis of 2D EXCSY spectra that the metal ion is rigidly locked to the inside surface of the carbon cage (Rübsam et al, 1996). In the present case of encapsulated NO radical it was concluded from the broad variance of its principal g matrix values (Hasegawa et al, 2018a) that even at low temperatures the radical is not fixed to a particular site. It was remarkable that the very small value quoted for the axial component (Hasegawa et al, 2018a) of 1 https://doi.org/10.5194/mr-2020-11…”

Section: Introductionmentioning

confidence: 67%

“…In a series of recent publications, the Kyoto group has shown that it is possible to encapsulate small and even reactive molecules in a modified C 60 cage with tailored entrance and exit holes (Hasegawa et al, 2018a;Futagoishi et al, 2017;Hashikawa et al, 2018). Using such designer type open cages instead of closed structures creates a new route for the preparation of interesting compounds.…”

Section: Introductionmentioning

confidence: 99%

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EPR Study of NO radicals encased in modified open C60 Fullerenes

Dinse¹,

Kato²,

Hasegawa³

et al. 2020

Preprint

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Abstract. Using pulsed EPR techniques, the low temperature magnetic properties of the NO radical being confined in a C60 derived cage are determined. It is found that the smallest principal g value g3, being assigned to the axis of the radical, deviates strongly from the free electron value. This behavior results from partial compensation of the spin and orbital contributions to the g3 value. The measured value g3 = 0.77(5) yields information about the deviation of the locking potential from axial symmetry. This 17 meV asymmetry is found to be quite small compared to the situation found for the same radical in polycrystalline or amorphous matrices ranging from 300 to 500 meV. The analysis of the temperature dependence of spin relaxation times resulted in a critical temperature of about 3.5 K, assigned to temperature activated motion of the radical with coupled rotational and translational degrees of freedom in the complicated 3-dimensional potential.

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Section: Introductionmentioning

confidence: 60%

Section: Introductionmentioning

confidence: 67%

Section: Introductionmentioning

confidence: 99%

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EPR Study of NO radicals encased in modified open C60 Fullerenes

Dinse¹,

Kato²,

Hasegawa³

et al. 2020

Preprint

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“…Subsequently, by encapsulating a NO molecule into an open‐cage fullerene derivative, a metal‐free electron spin system was successfully constructed. [ 16 ] The synthetic methods to insert small molecules into fullerene derivatives have been extensively studied. [ 17 ] Very recently, Han et.…”

Section: Introductionmentioning

confidence: 99%

Highly Sensitive and Selective Sensors for CF₄ Gas Molecules Based on Two‐Node Hollow Fullerene

Zhang

Feng

et al. 2020

Adv Materials Inter

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assemblies and nanofunctional materials in the field of optoelectronic devices, catalysis, biomedicines, and so on. [4] On one hand, C 60 has a triple degenerate lowest unoccupied molecule orbital (LUMO), presenting a good electron-accepting ability for holding up to six electrons and facilitating the formation of donor-acceptor dyads. On the other hand, it can be viewed as electron-deficient polyalkene and, therefore, chemically reactive. [5] These two features make the derivatization of fullerene feasible so as to extend its functionality. Various kinds of molecules/ structures have been linked to fullerenes to form fullerenes derivatives. For example, biphenyl fulleroids (Ph 2 C 61) was first synthesized by Suzuki et al. in 1991, [6] which was followed soon by the synthesis of Phenyl-C61-butyric acid methyl ester (PC 61 BM). [7] The latter was demonstrated advantageous in organic photovoltaics (OPVs) by enhancing the open-circuit voltage. [8] Meanwhile, physical and chemical modifications of fullerene have been achieved by linking to other molecular structures. By combining the distinctive features of fullerenes and unique physical properties of the linked molecules, advanced fullerene derivative materials with novel physicochemical characteristics can be synthesized. Some of these fullerene derivative materials have been demonstrated to possess great electrical, [9] thermal, [10] optical, [11] photovoltaic, [12] and solubility properties, [12] which could be applied in photovoltaic, [13] optical, [10c] and temperature sensors. [14] The cage-shaped space of fullerene derivatives can be used to trap small molecules. These small molecules, in turn, modify the electronic properties of the fullerene derivatives, leading to various structures of the fullerene derivatives with peculiar and exceptional phenomenon. The design and development of such molecular containers with a discrete structure for the uptake of small molecules represent attractive research targets. Recently, the synthesis of open-cage fullerene with a circular 17-membered-ring opening, which contains one sulfur atom on the rim, was reported. [15] Murata and co-workers trapped N 2 and CO 2 molecules in the confined internal sub-nano spaces of the open-cage fullerene derivatives. Subsequently, by encapsulating a NO molecule into an open-cage fullerene derivative, a metal-free electron spin system was successfully constructed. [16] The synthetic methods to insert small molecules into fullerene derivatives have been extensively studied. [17] Very recently, Han et. al., synthesized a variety of hollow C 60 nanostructures, using the xylene template, with tailored shapes, such as two-node calabash. [18] This methodology not only expands the synthetic Hollow nanostructures are widely used in chemistry, materials, and bioscience due to their excellent electrochemical and photoelectric properties. Recently, hollow fullerene nanostructures with tailored opening and shapes have been synthesized. Here, the transport properties of two-node hollow-fullerene-based ...

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“…[19][20][21][22][23][24] The16-membered orifice of 2 is too small to allow entry of bigger guests,b ut these can be accommodated by the larger (17-membered) opening of fullerene 3. [25] Insertion of N 2 and CO 2 , [26] CH 3 OH and H 2 CO, [27] CH 4 and NH 3 , [28] NO, [29] and O 2 , [30] into 3 have all been recently described, but aprocedure for suturing the opening of A@3 to give A@C 60 has not yet been reported. In this article,w ed escribe the successful closure of A@3 to give A@C 60 .Thee ndohedral fullerenes H 2 @C 60 and H 2 O@C 60 are exceptional platforms for the study of nuclear spin isomer-Figure 1.…”

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First Synthesis and Characterization of CH₄@C₆₀

et al. 2019

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The endohedral fullerene CH 4 @C 60 ,i nw hich each C 60 fullerene cage encapsulates asingle methane molecule,has been synthesized for the first time.Methane is the first organic molecule,a swella st he largest, to have been encapsulated in C 60 to date.T he key orifice contraction step,aphotochemical desulfinylation of an open fullerene,w as completed, even though it is inhibited by the endohedral molecule.T he crystal structure of the nickel(II) octaethylporphyrin/ benzenesolvate shows no significant distortion of the carbon cage,r elative to the C 60 analogue,and shows the methane hydrogens as ashell of electron density around the central carbon, indicative of the quantum nature of the methane.The 1 Hspin-lattice relaxation times (T 1 )f or endohedral methane are similar to those observed in the gas phase,i ndicating that methane is freely rotating inside the C 60 cage.T he synthesis of CH 4 @C 60 opens ar oute to endofullerenes incorporating large guest molecules and atoms.Soon after the discovery of C 60 in 1985, [1] came recognition that its approximately spherical 3.7 diameter cavity provides aunique environment in which to isolate single atoms. [2] Since then endohedral fullerenes,that is,compounds denoted A@C 60 in which molecules or atoms are enclosed within the fullerene cage,have been the focus of substantial experimental and theoretical efforts. [3][4][5] Endohedral fullerenes may be synthesized by forming the fullerene in the presence of the endohedral species (particularly successful for metallofullerenes), [3,5] by high temperature and pressure treatment of the fullerene with the endohedral species (inert gas@C 60 ), [6,7] or by ion bombardment of the fullerene (N@C 60 ), [8] but all give very low incorporation and require extensive purification. Furthermore,t hese methods are not applicable to the incorporation of small organic molecules.Them acroscopic-scale preparation of endohedral fullerenes by multi-step "molecular surgery" [9][10][11][12] involves chemically opening an orifice in the fullerene,o fas ize suitable to allow entry of the single molecule.S uturing of this orifice to restore the pristine carbon cage was pioneered by Komatsu [13,14] and Murata [15] who reported the first syntheses of H 2 @C 60 and H 2 O@C 60 following insertion of H 2 or H 2 O under high-pressure,i nto open-cage fullerenes 1 and 2, respectively.O ptimized procedures for the synthesis of H 2 @C 60 and H 2 O@C 60 have subsequently been reported by ourselves, [16] based on Murataso pen-cage C 60 derivative 2, and also applied to the synthesis of HF@C 60 (Figure 1). [17,18] Them acroscopic quantities of endohedral fullerenes provided by molecular surgery have allowed detailed investigation of physical properties,i ncluding by neutron scattering, infrared spectroscopy,a nd NMR spectroscopy. [19] These methods have shown that, as ar esult of the inert and highly symmetrical environment of the cavity,a ne ntrapped molecule behaves much as would be expected in the very lowpressure gas state, [17,[19][20][21][22][23] displ...

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Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C₆₀ Derivative

Cited by 30 publications

References 47 publications

EPR Study of NO radicals encased in modified open C60 Fullerenes

EPR Study of NO radicals encased in modified open C60 Fullerenes

Highly Sensitive and Selective Sensors for CF₄ Gas Molecules Based on Two‐Node Hollow Fullerene

First Synthesis and Characterization of CH₄@C₆₀

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Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C60 Derivative

Cited by 30 publications

References 47 publications

EPR Study of NO radicals encased in modified open C60 Fullerenes

EPR Study of NO radicals encased in modified open C60 Fullerenes

Highly Sensitive and Selective Sensors for CF4 Gas Molecules Based on Two‐Node Hollow Fullerene

First Synthesis and Characterization of CH4@C60

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Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C₆₀ Derivative

Highly Sensitive and Selective Sensors for CF₄ Gas Molecules Based on Two‐Node Hollow Fullerene

First Synthesis and Characterization of CH₄@C₆₀