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Azafullerenes derived from nitrogen substitution of carbon cage atoms render direct modifications of the cage skeleton, electronic, and physicochemical properties of fullerene. Gas-phase ionized monometallic endohedral azafullerene (MEAF) [La@C

Hundreds of members have been synthesized and versatile applications have been promised for endofullerenes (EFs) in the past 30 y. However, the formation mechanism of EFs is still a long-standing puzzle to chemists, especially the mechanism of embedding clusters into charged carbon cages. Here, based on synthesis and structures of two representative vanadium–scandium–carbido/carbide EFs, VSc 2 C@ I h (7)-C 80 and VSc 2 C 2 @ I h (7)-C 80 , a reasonable mechanism—C 1 implantation (a carbon atom is implanted into carbon cage)—is proposed to interpret the evolution from VSc 2 C carbido to VSc 2 C 2 carbide cluster. Supported by theoretical calculations together with crystallographic characterization, the single electron on vanadium (V) in VSc 2 C@ I h (7)-C 80 is proved to facilitate the C 1 implantation. While the V=C double bond is identified for VSc 2 C@ I h (7)-C 80 , after C 1 implantation the distance between V and C atoms in VSc 2 C 2 @ I h (7)-C 80 falls into the range of single bond lengths as previously shown in typical V-based organometallic complexes. This work exemplifies in situ self-driven implantation of an outer carbon atom into a charged carbon cage, which is different from previous heterogeneous implantation of nonmetal atoms (Group-V or -VIII atoms) driven by high-energy ion bombardment or high-pressure offline, and the proposed C 1 implantation mechanism represents a heretofore unknown metal–carbon cluster encapsulation mechanism and can be the fundamental basis for EF family genesis.

The reaction of μ3-CCF Dy2TiC@Ih-C80 with AdN2 affords only one [6,6]-open monoadduct along with the addition sites adjacent to the Ti4+ ion instead of the two Dy3+ ions, revealing the decisive role of the non-rare earth metal Ti(IV).

Monometallic cyanide clusterfullerenes (CYCFs) represent a unique branch of endohedral clusterfullerenes with merely one metal atom encapsulated, offering a model system for elucidating structure-property correlation, while up to now only C82 and C76 cages have been isolated for the pristine CYCFs. C84 is one of the most abundant fullerenes and has 24 isomers obeying the isolated pentagon rule (IPR), among which 14 isomers have been already isolated, whereas the C2v(17)-C84 isomer has lower relative energy than several isolated isomers but never been found for empty and endohedral fullerenes. Herein, four novel C84-based pristine CYCFs with variable encapsulated metals and isomeric cages, including MCN@C2(13)-C84 (M = Y, Dy, Tb) and DyCN@C2v(17)-C84, have been synthesized and isolated, fulfilling the first identification of the missing C2v(17)-C84 isomer, which can be interconverted from the C2(13)-C84 isomer through two steps of Stone-Wales transformation. The molecular structures of these four C84-based CYCFs are determined unambiguously by single-crystal X-ray diffraction. Surprisingly, although the ionic radii of Y3+, Dy3+, and Tb3+ differ slightly by only 0.01 A, such a subtle difference leads to an obvious change in the metal-cage interactions, as inferred from the distance between the metal atom and the nearest hexagon center of the C2(13)-C84 cage. On the other hand, upon altering the isomeric cage from DyCN@C2(13)-C84 to DyCN@C2v(17)-C84, the Dy-cage distance changes as well, indicating the interplay between the encapsulated DyCN cluster and the outer cage. Therefore, we demonstrate that the metal-cage interactions within CYCFs can be steered via both internal and external routes.

Endohedral clusterfullerenes exhibit unique chemical properties due to intramolecular electron transfer of the encaged metal cluster to the outer fullerene cages. Herein, we report the synthesis of two Sc 3 N@ D 3 h -C 78 monoadducts 2a and 2b through the 1, 3-dipolar reaction of Sc 3 N@ D 3 h -C 78 with carbonyl ylide bearing anomalous cis-conformation regioselectivity. The molecular structures of these monoadducts are unambiguously confirmed by single-crystal X-ray crystallography, revealing that both of 2a and 2b have cis-conformations within furan moiety grafted via [6,6]-closed addition patterns. Under the same conditions, the control reaction of C 60 with carbonyl ylide affords two monoadducts 3a and 3b , which however exhibit respectively the cis - and trans -conformations with [6,6]-closed addition patterns. According to theoretical calculations, the exclusive formation of the cis -only Sc 3 N@ D 3 h -C 78 monoadducts is interpreted by the conjunct effects of thermodynamic stability of adducts, the reactivity of the addition site, and the cis-dipole intermediate from trans 1 .

To date, the experimental studies on Nd-based metallofullerenes are only limited to spectroscopic characterizations. In this work, the molecular structures of Nd@C82(I,II) isomers, including the isomeric symmetry of the C cage and the position of endohedral Nd atom, as well as their unique two-dimensional (2D)-layered crystallographic packing structures were initially and unambiguously elucidated, based on the X-ray structural analyses of the cocrystals of Nd@C82(I) or Nd@C82(II) with cocrystallizing agent decapyrrylcorannulene (DPC). In the V-shaped unit cell, the endohedral Nd atom prefers a site as far away from the DPC molecules as possible because of the unevenly distributed charge on the C cage mainly related to the charge transfers from the endohedral Nd atom, cocrystallizing agent DPC, and solvent toluene molecules to the C82 cage. Apart from charge transfers, multiple C-H···π intermolecular interactions are also confirmed to play important roles both for the orientation of the C cage correlated with the preferential sites of the endohedral Nd atom and for the 2D-layered packing structures within the cocrystals. Density functional theory computations offered theoretical support for the molecular structures of Nd@C82(I,II) isomers, the valence of the endohedral Nd atom (between II+ and III+), and the global ground state, i.e., the Nd@C2v(9)-C82 isomer in the quintet state.

Endohedral clusterfullerenes featuring the encapsulation of metal clusters within carbon cages exhibit intriguing physical and chemical properties inaccessible to empty fullerenes. Thus far, their syntheses are predominantly fulfilled by using gaseous sources, suffering from low yield, and requiring an additional gas inlet and a heating pretreatment up to 1000 °C. Herein, we employ an ancient pigment, Prussian blue (Fe4[Fe(CN)6]3), as a cheap solid cyanide/nitrogen dual-source, affording the simplified yet high-yield simultaneous syntheses of novel dysprosium (Dy)-based metal cyanide clusterfullerenes (CYCFs) DyCN@C2n and metal nitride clusterfullerenes Dy3N@C2n. Surprisingly, the (CN)− anion of Fe4[Fe(CN)6]3 survives under the extremely high temperature (up to 4000 K) of plasma generated via DC-arc discharge, and functions as the cyanide source of CYCFs. Under the optimized Dy : [CN] : C molar ratio of 1 : 1 : 15, the sum yield of isolated DyCN@C2n (2n = 76, 82) CYCFs produced using Fe4[Fe(CN)6]3 is about 2.8 times higher than that obtained using gaseous N2 source. Moreover, the molecular structures of the three isomers of DyCN@C82 are unambiguously determined by single-crystal X-ray diffraction, indicating that the encapsulated triangular DyCN cluster is tunable due to strong metal–cage interactions. This study paves the way for the low-cost and high-yield syntheses of pricey endohedral fullerenes.

Trimetallic carbide clusterfullerenes (TCCFs) encapsulating a quinary M3C2 cluster represent a special family of endohedral fullerenes with an open-shell electronic configuration. Herein, a novel TCCF based on a medium-sized rare earth metal, dysprosium (Dy), is synthesized for the first time. The molecular structure of Dy3C2@Ih(7)-C80 determined by single crystal X-ray diffraction shows that the encapsulated Dy3C2 cluster adopts a bat ray configuration, in which the acetylide unit C2 is elevated above the Dy3 plane by ∼1.66 Å, while Dy–Dy distances are ∼3.4 Å. DFT computational analysis of the electronic structure reveals that the endohedral cluster has an unusual formal charge distribution of (Dy3)8+(C2)2−@C806− and features an unprecedented three-center single-electron Dy–Dy–Dy bond, which has never been reported for lanthanide compounds. Moreover, this electronic structure is different from that of the analogous Sc3C2@Ih(7)-C80 with a (Sc3)9+(C2)3−@C806− charge distribution and no metal–metal bonding., A novel trimetallic carbide clusterfullerene, Dy3C2@Ih(7)-C80, was successfully synthesized and isolated, and the encapsulated Dy3C2 cluster adopts a bat ray configuration featuring an unprecedented three-center single-electron Dy–Dy–Dy bond.

Porous carbon materials play essential roles in electrocatalysis and electrochemical energy storage. It is of significant importance to rationally design and tune their porous structure and active sites for achieving high electrochemical activity and stability. Herein, we develop a novel approach to tune the morphology of porous carbon materials (PCM) by embedding fullerene C60, achieving improved performance of oxygen reduction reaction (ORR) and lithium-sulfur (Li-S) battery. Owing to the strong interaction between C60 and imidazole moieties, pomegranate-like hybrid of C60-embedded zeolitic imidazolate framework (ZIF-67) precursor is synthesized, which is further pyrolyzed to form C60-embedded cobalt/nitrogen-codoped porous carbon materials (abbreviated as C60@Co-N-PCM). Remarkably, the unique structure of C60@Co-N-PCM offers excellent ORR electrocatalytic activity and stability in alkaline solutions, outperforming the commercial Pt/C (20 wt.%) catalyst. Besides, C60@Co-N-PCM as a novel cathode delivers a high specific capacity of ∼ 900 mAh·g−1 at 0.2 C rate in Li-S batteries, which is superior to the pristine ZIF-67-derived PCM without embedding C60.

The family of experimentally confirmed isolated-pentagon-rule (IPR) isomers of C96 fullerene is extended by trifluoromethylation of a C96 fraction of the fullerene soot, high-performance liquid chromatography separation of CF3 derivatives, and a single-crystal X-ray diffraction study of C96(CF3)n compounds with the use of synchrotron radiation. New cage isomers were revealed in C96(94)(CF3)18/20 and C96(182)(CF3)18 compounds, whereas isomer C96(181), previously known in the adduct with nickel porphyrinate, was confirmed in C96(181)(CF3)18/20 derivatives. Common and special features of the addition patterns of CF3 groups on C96 carbon cages are discussed in more detail. The investigated isomers belong to the most stable C2-C96(181) and slightly less stable C1-C96(94) and C2-C96(182) among the altogether 15 experimentally confirmed IPR isomers of C96 fullerene.

Nanoscale magnetic materials have been attracting enormous interests during the past few decades due to the rapid development of high-density magnetic storage devices. A breakthrough in nanomagnetism is the discovery of single molecule magnets (SMMs), which exhibit slow relaxation and quantum tunneling of the magnetization resulted from a molecular-based blocking anisotropy, and thus have potential applications in high-density data storage, molecular spintronics and quantum computing. Since the report of Mn12-complex as the first SMM by Sessoli et al. in 1993, a large number of SMMs based on organometallic coordination compounds have been synthesized. Compared to the traditional bulk magnets, the magnetic properties of SMMs are determined by their instrinsic spin structures resulting in slow magnetic relaxation. SMM is characterized by a bi-stable magnetic ground state and a certain spin-reversal barrier ( U eff). Additionally, hysteresis loops can be observed below the blocking temperature ( T B). Therefore, SMMs with excellent magnetic properties always have high T B and U eff. U eff depends strongly on spin ground state ( S ) and magneto-crystalline anisotropy ( D ), and can be expressed with the formula U eff =| D|S 2. For transition metal-based SMMs, their low magneto-crystalline anisotropies ( D ) result in relative low U eff. In recent years, lanthanide based SMMs have been studied intensively and become the most promising high-performance SMMs, owning to their strong single ion anisotropy. Encapsulating metal atoms or metallic clusters into fullerene cages generate a special class of fullerenes, the so-called endohedral metallofullerenes (EMFs), for which the encapsulation of metal atoms endow EMFs more fascinating properties compared to empty fullerenes. For instance, EMFs are paramagnetic when the entrapped metal ions have unpaired electrons. Furthermore, EMFs were able to show excellent SMM properties when the encapsulated clusters induce appropriate ligand-fields. EMFs with lanthanide open up a new avenue in the field of SMMs in 2012 when single molecule magnetism was proved for the metal nitride clusterfullerene (NCF) DySc2N@ I h-C80. Fullerene cages are stable in air and thus they can protect the magnetic ions from ambient conditions, and the negatively charged nonmetallic atom(s) within the cluster and the negatively charged carbon atoms of fullerene cages provide magnetic anisotropy which is necessary for single molecule magnetism. Moreover, the molecular structures of EMFs can be modulated by varying the encapsulated metal ions, metal cluster and cage isomer; hence the research on EMF-SMMs has been developed rapidly since 2012. Up to now, metal nitride clusterfullerenes (NCFs), metal carbide clusterfullerenes (CCFs), metal oxide clusterfullerenes (OCFs), metal sulfide clusterfullerenes (SCFs), metal cyanide clusterfullerenes (CYCFs) and dimetallofullerenes (di-EMFs) have been confirmed as SMMs. In this paper, we present an exhaustive review on all kinds of EMF-SMMs reported to date including their 1D, 2D and 3D assemblies. We mainly discuss the influences of the types and the numbers of the encapsulated metal ions and non-metal atoms on the magnetic properties of EMF-SMMs. Finally, the prospects and challenges of EMF-SMMs are also discussed.

Data concerning the isomeric composition of C98 and the chemistry of C98 derivatives are scarce due to very low abundance of C98 in the fullerene soot. Trifluoromethylation of C98 -containing mixtures followed by HPLC separation of CF3 derivatives and single crystal X-ray diffraction study resulted in structural characterization of four compounds C98 (248)(CF3 )18/20 , C98 (116)(CF3 )18 , and C98 (120)(CF3 )20 . To date, these compounds represent the largest fullerenes isolated as CF3 derivatives with experimentally determined molecular structures. The addition patterns of C98 (CF3 )18/20 are discussed in detail revealing the stabilizing factors, such as isolated double C=C bonds and benzenoid rings on C98 fullerene cages. A detailed comparison with the addition patterns of the known C98 Cln allowed us to contribute to the better understanding the chemistry of elusive C98 fullerene.

According to the isolated pentagon rule (IPR), for stable fullerenes, the 12 pentagons should be isolated from one another by hexagons, otherwise the fused pentagons will result in an increase in the local steric strain of the fullerene cage. However, the successful isolation of more than 100 endohedral and exohedral fullerenes containing fused pentagons over the past 20 years has shown that strain release of fused pentagons in fullerene cages is feasible. Herein, we present a general overview on fused-pentagon-containing (i.e. non-IPR) fullerenes through an exhaustive review of all the types of fused-pentagon-containing fullerenes reported to date. We clarify how the strain of fused pentagons can be released in different manners, and provide an in-depth understanding of the role of fused pentagons in the stability, electronic properties, and chemical reactivity of fullerene cages.

Despite recent successes in preparing three-dimensional crystals of empty fullerenes, such as C60 and C70 , 3D endohedral fullerene crystals, and especially hollow nanostructures, have been scarcely reported. A universal approach has now been developed to prepare shape-tunable 3D crystals of several metal nitride clusterfullerenes, including cubes and dice (hollow cubes with holes at the center of each face), which can be readily switched by changing the volume ratio of good (mesitylene) and poor (isopropanol) solvents. Synchrotron-based soft X-ray nano-computed tomography was used to unambiguously identify the interior microstructure of the dice-shaped crystals of Tb3 N@C80 , and especially the depth of the hole at each face, confirming that the dice has a solid center and the holes are not interconnected. Owing to the enhanced light absorption, the dice-shaped crystals exhibit enhanced photoluminescence relative to that of the cubes.

High-temperature trifluoromethylation of isolated-pentagon-rule (IPR) fullerene C92 chlorination products followed by HPLC separation of C92 (CF3 )n derivatives resulted in the isolation and X-ray structural characterization of IPR C92 (38)(CF3 )18 and non-classical C92 (NC)(CF3 )22 . The formation of C92 (38)(CF3 )18 as the highest CF3 derivative of the known isomer C92 (38) can be expected. The formation of C92 (NC)(CF3 )22 was interpreted as chlorination-promoted cage transformation of C92 (38) followed by trifluoromethylation of non-classical C92 (NC) chloride. Noticeably, C92 (NC)(CF3 )22 shows the highest degree of trifluoromethylation among all known CF3 derivatives of fullerenes. The addition patterns of C92 (38)(CF3 )18 and C92 (NC)(CF3 )22 are discussed and compared to the chlorination patterns of C92 (38)Cln compounds.

High-temperature chlorination of C92 fractions, followed by single-crystal X-ray diffraction, resulted in the structure determination of C92(38)Cl18, C92(38)Cl22, C92(26)Cl24, nonclassical C90( NC)Cl22, and non-isolated-pentagon-rule C90Cl26. Two latter chloro derivatives were obtained by chlorination-promoted cage transformations via a single C2 loss from C92(50) and a combination of a C2 loss from C92(23) and three Stone-Wales rearrangements. The chlorination patterns are stabilized by the formation of isolated C═C bonds and aromatic substructures on carbon cages. The presence of C92 isomer numbers 23, 26, and 50 in the arc-discharge fullerene soot has been confirmed for the first time.

Monometallic cyanide clusterfullerenes (CYCFs) represent a unique branch of endohedral clusterfullerenes with merely one metal atom encapsulated, offering a model system for elucidating structure-property correlation, while up to now only C

To date, the experimental studies on Nd-based metallofullerenes are only limited to spectroscopic characterizations. In this work, the molecular structures of Nd@C

Endohedral clusterfullerenes exhibit unique chemical properties due to intramolecular electron transfer of the encaged metal cluster to the outer fullerene cages. We report the synthesis of two Sc

The family of experimentally confirmed isolated-pentagon-rule (IPR) isomers of C

Few-layer black phosphorus (BP) with an anisotropic two-dimensional (2D)-layered structure shows potential applications in photoelectric conversion and photocatalysis, but is easily oxidized under ambient condition preferentially at its edge sites. Improving the ambient stability of BP nanosheets has been fulfilled by chemical functionalization, however this functionalization is typically non-selective. Here we show that edge-selective functionalization of BP nanosheets by covalently bonding stable C60 molecules leads to its significant stability improvement. Owing to the high stability of the hydrophobic C60 molecule, C60 functions as a sacrificial shield and effectively protects BP nanosheets from oxidation under ambient condition. C60 bonding leads to a rapid photoinduced electron transfer from BP to C60, affording enhanced photoelectrochemical and photocatalytic activities. The selective passivation of the reactive edge sites of BP nanosheets by sacrificial C60 molecules paves the way toward ambient processing and applications of BP.

Molybdenum disulfide (MoS2) as a representative transition-metal dichalcogenide (TMD) has been extensively used as a noble-metal-free cocatalyst for photocatalytic hydrogen (H2) production, but suffers from poor photocatalytic activity due to the catalytic inactivity of its basal plane. Herein, by bounding another metal-free cocatalyst, C60, with MoS2, we report the first MoS2-C60 hybrid featuring a van der Waals heterostructure prepared via a facile and eco-friendly solid-state mechanochemical route. C60 bounding onto the edge of MoS2 nanosheets leads to the decreases of both the number of layers and the size of MoS2 nanosheets, as well as a negative shift of the conduction band minimum along with a positive shift of valance band maximum relative to the bulk MoS2 and MoS2 ball-milled without C60 (MoS2-BM). Under the optimized weight ratio of MoS2:C60 (1:1) in the raw mixture subject to ball-milling, MoS2-C60 hybrid containing 2.8 wt% C60 shows an exceptional visible light photocatalytic H2 production rate of 6.89 mmol h−1 g−1 in the presence of a photosensitizer Eosin Y (EY), which is significantly enhanced relative to the bulk MoS2 and pristine C60, both of which show almost no photocatalytic H2 activity. Thus, the synergistic enhancement of photocatalytic activities of both MoS2 and C60 is revealed.

Rare-earth metals have been mostly entrapped into fullerene cages to form endohedral clusterfullerenes, whereas non-Group-3 transition metals that can form clusterfullerenes are limited to titanium (Ti) and vanadium (V), and both are exclusively entrapped within an Ih -C80 cage. Non-Group-3 transition-metal-containing endohedral fullerenes based on a C80 cage with D5h symmetry, Vx Sc3-x N@D5h -C80 (x=1, 2), have now been synthesized, which exhibit two variable cluster compositions. The molecular structure of VSc2 N@D5h -C80 was unambiguously determined by X-ray crystallography. According to a comparative study with the reported Ti- and V-containing clusterfullerenes based on a Ih -C80 cage and the analogous D5h -C80 -based metal nitride clusterfullerenes containing rare-earth metals only, the decisive role of the non-Group-3 transition metal on the formation of the corresponding D5h -C80 -based clusterfullerenes is unraveled.

Data concerning the isomeric composition of C

High-temperature chlorination of C

Fullerene has a definite 0D closed‐cage molecular structure composed of merely sp2‐hybridized carbon atoms, enabling it to serve as an important building block that is useful for constructing supramolecular assemblies and micro/nanofunctional materials. Conversely, graphene has a 2D layered structure, possessing an exceptionally large specific surface area and high carrier mobility. Likewise, other emerging graphene‐analogous 2D nanomaterials, such as graphitic carbon nitride (g‐C3N4), transition‐metal dichalcogenides (TMDs), hexagonal boron nitride (h‐BN), and black phosphorus (BP), show unique electronic, physical, and chemical properties, which, however, exist only in the form of a monolayer and are typically anisotropic, limiting their applications. Upon hybridization with fullerenes, noncovalently or covalently, the physical/chemical properties of 2D nanomaterials can be tailored and, in most cases, improved, significantly extending their functionalities and applications. Here, an exhaustive review of all types of hybrids of fullerenes and 2D nanomaterials, such as graphene, g‐C3N4, TMDs, h‐BN, and BP, including their preparations, structures, properties, and applications, is presented. Finally, the prospects of fullerene‐2D nanomaterial hybrids, especially the opportunity of creating unknown functional materials by means of hybridization, are envisioned.

A red phosphor of Eu3+, Bi3+ co-doped Sr3Ga2O5Cl2 is synthesized by solid-state reaction for the first time. The XRD Rietveld refinement presents that the compound crystallizes in a monoclinic crystal system with space group C 2 2 − P 2 1 . Under the excitation of 393 nm, Sr3Ga2O5Cl2:Eu3+ shows an efficient red emission with the dominated peak at 618 nm (5D0–7F2). With the introduction of Bi3+, the emission intensity of Eu3+ rapidly increases due to the energy transfer from Bi3+ to Eu3+. The dominated emission peak shifts from 618 to 703 nm (5D0–7F4), implying that the crystal environment of Eu3+ in Sr3Ga2O5Cl2 possibly becomes serious distortion. With the increase of temperature from 20 to 250 °C, the Eu3+ single doped Sr3Ga2O5Cl2 reveals an excellent thermal property, but the thermal stability of Eu3+, Bi3+ co-doped Sr3Ga2O5Cl2 appears severe degradation, which indicate that a complicated energy transfer process possibly occurs between Eu3+ and Bi3+. Based on the configurational coordinate diagram, the phenomenon can be reasonably explained.

A red-emitting phosphor MgY4Si3O13:Eu3+ was synthesized by conventional solid-state reaction for the first time. Photoluminescence spectra show that the phosphor can be efficiently excited by ultraviolet and blue light and exhibit an intense emission at 615 nm due to the dominant 5D0→7F2 electric dipole transition of Eu3+. The decay times of Eu3+ monitored at the different wavelengths present an interesting change trend. According to the results of XRD Rietveld refinement, in a unit cell, the number of Eu3+ is obtained to be 0.064 for 4f site and 0.294 for 6 h site. The remarkable preference occupancy for one site could be the leading reason of the abnormal change in decay times. The testing of thermal quenching indicates that the photoluminescence intensity of the phosphor is very sensitive to temperature and furthermore, the emission intensities from 5D1→7FJ and 5D0→7FJ show the different decay ratios with the increase in temperature. Based on the configurational coordinate diagram, an underlying mechanism is proposed and can explain the phenomenon reasonably. The mechanism could be helpful for the understanding of the energy transfer phenomenon among the various energy levels in the process of temperature change as reference.

A single-phase white-light emitting phosphor MgY4Si3O13:Dy3+ was synthesized using the solid state method under reducing atmosphere and in air for the first time. Upon ultraviolet light excitation, the phosphor exhibits intense warm white light emission with optimal CIE chromaticity coordinates of 0.432 and 0.421 and a correlated color temperature value of 3160 K. The emission intensities of samples synthesized under the reducing atmosphere are superior to those in air due to the sensitization of host to Dy3+. With the increase in temperature, MgY4Si3O13:Dy3+ presents satisfactory thermal properties and based on the configurational coordinate diagram, the energy transfer mechanism between the host and Dy3+ is carefully investigated. All the results indicate that MgY4Si3O13:Dy3+ could be a promising phosphor for warm white UV-LEDs.

Endohedral metallofullerenes (EMFs) with entrapping atoms and clusters have many superior properties due to the electron transfer from inner clusters to outer carbon cages, enabling them numerous potential applications in the fields of single molecule magnet, energy conversion, nano devices. The chemical functionalization of endohedral metallofullerenes through attraching different functional groups onto fullerene cage is useful strategy to improve corresponding solubility and tune the electron structure of endohedral metallofullerenes. Due to lower cage symmetry of Sc3N@D3h -C78 relative to that of Sc3N@Ih -C80, the high regioseletive synthesis of Sc3N@D3h -C78 derivatives have been a challenge in the fields of fullerene chemistry, howeer, is highly desired. Herein, we performed a photoreaction of Sc3N@Ih -C78 with asymmetric aryl oxirane in the toluene solution, leading to only main product among the possible 34 isomers. The X-ray single crystal diffraction measurement shows the [6,6]-close addition pattern of Sc3N@Ih -C78 derivative.

By hybridizing covalently or noncovalently fullerenes with 2D nanomaterials such as graphene, molybdenum disulfide (MoS2) and black phosphorus (BP), the unique properties of 2D nanomaterials can be tailored and improved, significantly extending their functionalities and applications. In article number 1800941, Shangfeng Yang and co‐workers exhaustively review all types of hybrids of fullerenes and 2D nanomaterials, emphasizing their versatile hybridization strategies and applications.