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Burke, Brian; Chan, Jack; Williams, Keith A.; Fuhrer, Timothy J.; Fu, Wujun; Dorn, Harry C.; Puretzky, Alexander A.; Geohegan, David B.

doi:10.1103/physrevb.83.115457

Cited by 17 publications

(18 citation statements)

References 33 publications

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“…For other rare earth metal elements, CCMFs are also common, but a size effect occurs due to the strong interactions between the metallic cluster and the cage (Figure ). A thorough inspection of the reported compounds with a composition of M 2 C 2 @C 2 n reveals that the small Sc 2 C 2 cluster prefers to be encapsulated inside the cages smaller than C 88 , but the relatively large M 2 C 2 (M = Gd, Tb, and Y) clusters tend to choose either the non-isolated pentagon rule (non-IPR) C 1 (51383)-C 84 cage or the even larger D 3 (85)-C 92 cage. − These results indicate that the size matching between the encapsulated metallic cluster and the fullerene is an important factor determining the stability of the resultant EMFs.…”

Section: Bonding Inside Emfsmentioning

confidence: 99%

Bonding inside and outside Fullerene Cages

2018

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Concrete crystallographic results of endohedral metallofullerenes (EMFs) disclose that the bonding within the metallic clusters and the interactions between the metal ions and the cage carbon atoms, which are closely associated with the coordination ability of the metal ions, play essential roles in determining the stability, the molecular structure, and the chemical behavior of the hybrid EMF molecules, in addition to the previously recognized charge transfer from metal to cage. For the carbide cluster metallofullerenes, a "size effect" between the encapsulated metallic cluster and the fullerene cage has been suggested. Thus, through the geometric effect, a series of giant fullerenes (C-C) have been stabilized by encapsulating a large LaC cluster, which adopts different configurations in accordance with cage size and shape. Interestingly, the crystallographic analysis of LaC@ D(450)-C has led to the direct observation of the axial compression of short carbon nanotubes caused by the internal stress. Additionally, the defective C(816)-C cage is viewed to be a precursor that can transform into the other three ideal tubular fullerene cages, presenting crystallographic evidence for the top-down formation mechanism of fullerenes. Structural characterization of YC@C confirms a linear carbide cluster inside the large cage, indicative of a geometric effect of cage size on the bonding behavior of the internal cluster. Apart from the carbide realm, direct metal-metal bonding is observed between the two seemingly repulsive Lu ions in Lu@C, adding new insights into current coordination chemistry. Meanwhile, the bonding state between the metal ions inside the cage (e.g., in La@ I (7)-C) and even the configuration of the internal metallic cluster (e.g., in ScC@ I (7)-C) can be readily controlled by exohedral radical addition, illuminating their future applications as single molecule magnets and in electronics. In addition, observation of the unexpected dimerization between two paramagnetic Y@ C(6)-C molecules suggests a spin-induced bonding behavior, which depends closely on the cage geometry. In contrast, synergistic effect of both electronic and geometric parameters has led to the formation of the unprecedented [6,6,6]-Lewis acid-base adduct of ScN@ I (7)-C. However, introduction of an oxygen atom gives rise to the corresponding normal carbene adducts for both ScN@ I (7)-C and LuN@ I (7)-C, presenting an unexpected way of steric hindrance release. Remarkably, the Lewis acid-base complexation is demonstrated to be a facile way toward isomerically pure metallofullerene derivatives with surprisingly high regioselectivity and quantitative conversion yield for ScC@ C(8)-C. This Account aims to give an advanced summary of the recent achievements in research of EMFs, focusing mainly on the interplay between the internal metallic species and the surrounding cages through bond formation or cleavage. Perspectives suggesting the future developments of EMFs are also given in the last section.

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Section: Bonding Inside Emfsmentioning

confidence: 99%

Bonding inside and outside Fullerene Cages

2018

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“…The BWF interference effect involving the interactions of discrete phonon states and the electronic continuum has been studied extensively in carbon-based materials (graphite, graphene, and nanotubes) [49][50][51] and semiconductors. [52][53][54][55] However, there are limited reports of this effect in TMDs. This electron-phonon interaction effect manifests itself as an asymmetric broadening in the phonon line shape depending on the dopant (p-doped or n-doped) and is described by the asymmetric parameter (1/q BWF ).…”

Section: Resonance Effect: Bwf Interference Effectmentioning

confidence: 99%

“…It is known that the BWF asymmetric parameter is dependent on carrier concentration. Extensive research has been reported on doped porous silicon 55,59,60 and other bulk semiconducting materials. 52,53 Recently, the effect of doping on the electronic transport and phonon line shapes of TMDs has been reported experimentally 56,61,62 and theoretically.…”

Section: Effect Of Carrier Concentrationmentioning

confidence: 99%

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Investigating the phonon line shapes of TMDs: An analytical approach

Zhou

Adu

2020

J Raman Spectroscopy

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Several phenomena can affect the phonon bands of low-dimensional systems, and their proper assignment and interpretation are essential in elucidating their effect on electronic, optical, and optoelectronic properties. Using an analytical approach, we investigate the similarities and differences of the layered effect, the phonon confinement effect, the Breit-Wigner-Fano effect, the inhomogeneous heating effect, and disorder-induced effects in the phonon line shapes of WS 2 and MoS 2. The subtle differences and similarities are critical in making proper assignments and interpretations of the phonon line shapes and are useful as guidance in the behavior of phonon bands, particularly in TMDs, and more generally in low-dimensional systems.

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“…Its carbide nature was later further confirmed by the same group utilizing 13 C NMR combined with synchrotron X-ray structural studies. Likewise, di-EMFs based on the groups III and IV metal atoms, to date, have achieved excellent progress, for instance, Er 2 C 2 @C 82 , Gd 2 C 2 @C 2 n (2 n = 88–92), , Y 2 C 2 @C 2 n (2 n = 82, 84, 92, 100), − Ti 2 C 2 @C 78 , − Dy 2 C 2 @C 82 , Tm 2 C 2 @C 82 , Tb 2 C 2 @C 82 , Sc 2 C 2 @C 82 − and mixed metal carbide clusterfullerene ErYC 2 @C 82 , all of which are proven to be CCFs. An increasing number of facts have proved that much attention to the structural determination of di-EMFs with large carbon cages should be paid, such as Ti 2 C 80 , − Sc 2 C 82 , and so on, in that their simple endohedral forms M 2 @C n may not fulfill the stable geometry structure and closed-shell electronic configuration rule (CSECR).…”

Section: Introductionmentioning

confidence: 99%

Unmasking the Optimal Isomers of Ti₂C₈₄: Ti₂C₂@C₈₂ Instead of Ti₂@C₈₄

Zhao

et al. 2018

J. Phys. Chem. C

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Up to now, the controversies over the stable structures of endohedral di-metallofullerenes M2C n , whether M2@C n or M2C2@C n–2, have continued ceaselessly. Herein, to disclose the optimal structures of Ti2C84, density functional theory combined with statistical thermodynamic analysis is performed in detail and it turns out that isolated pentagon rule C82 with Ti2C2 inserted wins overwhelmingly and performs close-shell electronic structure after our detailed analysis. Furthermore, the stimulation of UV–vis–NIR absorption spectra of thermodynamics preferred isomers under polarizable continuum models shows better accordance to the experimental spectra to reconfirm our result again. And 13C NMR spectra of three more stable isomers are performed for further investigations on geometry structures. Last but not least, the electronic structures and various interactions of thermodynamically optimum structures are further revealed.

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Vibrational spectrum of the endohedralY2C2@C

Cited by 17 publications

References 33 publications

Bonding inside and outside Fullerene Cages

Bonding inside and outside Fullerene Cages

Investigating the phonon line shapes of TMDs: An analytical approach

Unmasking the Optimal Isomers of Ti₂C₈₄: Ti₂C₂@C₈₂ Instead of Ti₂@C₈₄

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Vibrational spectrum of the endohedralY2C2@C

Cited by 17 publications

References 33 publications

Bonding inside and outside Fullerene Cages

Bonding inside and outside Fullerene Cages

Investigating the phonon line shapes of TMDs: An analytical approach

Unmasking the Optimal Isomers of Ti2C84: Ti2C2@C82 Instead of Ti2@C84

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Unmasking the Optimal Isomers of Ti₂C₈₄: Ti₂C₂@C₈₂ Instead of Ti₂@C₈₄