Since the first proposal that fullerenes are capable of hosting atoms, ions, or clusters by late Smalley in 1985, tremendous examples endohedral metallofullerenes (EMFs) have been reported. Breaking dogma monometallofullerenes (mono-EMFs) always exist form M@C2n while clusterfullerenes require multiple (two to four) metal cations stabilize a cluster is unstable as single moiety, here we show an unprecedented monometallic clusterfullerene entrapping yttrium cyanide inside popular C82...

The geometries of fullerenes are governed by the isolated pentagon rule (IPR), which states that stable have each their 12 pentagons surrounded five hexagons. At dawn fullerene science, it was widely believed IPR would also be applicable for endohedral fullerenes. In 2000, idea altered discovery first non-IPR fullerenes, Sc2@C66 and Sc3N@C68. structural data were interpreted to indicate presence a pair doubly fused pentagons. However, structure has remained long-standing mystery, since is...

Abstract Fullerene derivatives with different addition patterns exhibit physical, chemical, and biological properties, which are important for fullerene applications. Novel rare 1,2,3,16‐functionalized [60]fullerene having a five‐membered heterocycle fused to [5,6]‐junction were obtained high regioselectivity by electrochemical derivatization of [60]fulleroindoline. The product structures determined spectroscopic data single‐crystal X‐ray analysis. was rationalized using theoretical calculations.

Single crystals of three soluble Yb@C82 isomers, namely, Yb@C2(5)-C82, Yb@Cs(6)-C82, and Yb@C2v(9)-C82, cocrystallized with NiII(octaethylporphyrin), allowed accurate crystallographic elucidation their molecular structures in terms both cage symmetry metal location. Multiple positions were found all these but the major sites some specific regions within cages. Specifically, Yb2+ ion prefers to reside close a hexagonal ring Yb@C2(5)-C82 Yb@C2v(9)-C82 [5,6,6]-junction carbon atom Yb@Cs(6)-C82....

Controlling the distance of addition site carbons is a simple method for controlling NIR PL and UCPL properties SWNTs.

Aim: In this study, the physicochemical properties of stearyl glycyrrhetinate/β-cyclodextrin (SG/βCD) and SG/γCD complexes were characterized, prepared using co-milling method. The molecular interactions within SG/CD also investigated nuclear magnetic resonance (NMR) measurements to determine mode interaction. Methods: Here, we evaluated SG with CDs by ground mixtures (GM SG/βCD or γCD = 1/1, 1/2). Results: Powder X-ray diffraction (PXRD) showed that characteristic CD peaks disappeared after...

Fullerenyl radicals can be generated by addition of a free radical to fullerene surface, nucleophilic followed one-electron oxidation, or thermal dissociation singly bonded dimers. However, fullerenyl are usually very reactive and generally cannot isolated. On the contrary, we have found that reactions dimetallic endofullerenes, La2@Ih-C80 La2@D5h-C80, with 3-chloro-5,6-diphenyltriazine resulted in mono-addition triazinyl cages yield isolable radicals. The unusual stability these arises from...

Metal positions in endohedral metallofullerenes (EMFs) are of special importance because their molecular symmetry and intrinsic properties strongly influenced by the location motion encapsulated metals. X-ray analyses cocrystals Gd@C2v(9)-C82 with nickelII octaethylporphyrin [NiII(OEP)] reveal that Gd3+ cation is off-center, being located under a hexagonal ring along 2-fold axis C2v(9)-C82 cage. This result sharp contrast to previous study, showing has an anomalous structure, metal...

The endohedral fullerene once erroneously identified as Sc3@C82 was recently shown to be Sc3C2@Ih-C80, the first example of an open-shell cluster metallofullerene. We herein report that benzyl bromide (1) reacts with Sc3C2@ Ih-C80 via a regioselective radical addition affords only one isomer adduct Sc3C2@Ih-C80(CH2C6H5) (2) in high yield. An X-ray crystallographic study 2 demonstrated moiety is singly bonded cage, which eliminates paramagnetism agreement ESR results. Interestingly, results...

Dibutylated single-walled carbon nanotubes (Bu-SWNTs-Bu) with varying degrees of functionalization were prepared by two-step reductive alkylation and subsequent thermal treatment. A new photoluminescence peak at around 1240 nm was observed increased drastically after the The results indicate that thermally treated Bu-SWNTs-Bu are promising NIR photoluminescent materials.

Abstract Although all the pure‐carbon fullerene isomers above C 60 reported to date comply with isolated pentagon rule (IPR), non‐IPR structures, which are expected have different properties from those of IPR species, obtainable either by exohedral modification or endohedral atom doping. This report describes isolation and characterization a new metallofullerene (EMF), La 2 @C 76 , has cage. The X‐ray crystallographic result for /[Ni II (OEP)] (OEP=octaethylporphyrin) cocrystal unambiguously...

Functionalization of endohedral metallofullerenes has been shown to differ depending on photochemical or thermal pathways. We report that Lu(3)N@I(h)-C(80) reacts with thermally generated bis(2,6-diethylphenyl)silylene high selectivity and forms monosilylated derivative 1b. Unexpectedly, 1b undergoes conversion afford isomer 1a under ambient light. These adducts were characterized using NMR, visible-near-IR spectroscopy, matrix-assisted laser desorption ionization time-of-flight mass...

Fullerene crystals or films have drawn much interest because they are good candidates for use in the construction of electronic devices. The results theoretical calculations revealed that conductivity properties I(h)-C(80) endohedral metallofullerenes (EMFs) vary depending on encapsulated metal species. We experimentally investigated solid-state structures and charge-carrier mobilities EMFs La(2)@C(80), Sc(3)N@C(80), Sc(3)C(2)@C(80). thin film Sc(3)C(2)@C(80) exhibits a high electron...

Endohedral metallofullerenes (EMFs) encapsulating divalent metal ions have received limited attention because of their low production yields. Here, we report the results structural determination and chemical functionalization a typical metallofullerene, Yb@C84(II). Single-crystal X-ray crystallographic studies Yb@C84/Ni(II)(OEP) cocrystals (OEP is dianion octaethylporphyrin) unambiguously established chiral C2(13)-C84 cage structure revealed multiple sites for Yb(2+), indicating moving ion...

Abstract We report that Ce@ C 2 v (9)‐C 82 forms a centrosymmetric dimer when co‐crystallized with Ni(OEP) (OEP = octaethylporphyrin dianion). The crystal structure of {Ce@ } ⋅2[Ni(OEP)]⋅4 6 H shows new C−C bond length 1.605(5) Å connects the two cages. high spin density singly occupied molecular orbital (SOMO) on cage and pyramidalization are factors favor dimerization. In contrast, treatment M@ (M La, Sc, Y) results in crystallization monomeric endohedral fullerenes. A systematic...

We compared the chemical reactivity of D2d(23)-C84 and that Sc2C2@D2d(23)-C84, both having same carbon cage geometry, in photolysis 2-adamantane-2,3′-[3H]-diazirine, to clarify metal-atom doping effects on cage. Experimental computational studies have revealed is altered drastically by endohedral Sc2C2 doping. The reaction empty with diazirine under photoirradiation yields two adamantylidene (Ad) adducts. NMR spectroscopic major Ad monoadduct (C84(Ad)-A) has a fulleroid structure minor...

Abstract The dynamic positions of the dimetallic cluster inside mid‐sized spherical cages C 80 –C 82 have been seldom studied, despite high abundance M 2 @C n (2 =80, 82) species among various endohedral metallofullerenes. Herein, using crystallographic methods, we first unambiguously map metal for both Ce @ D 5 h ‐C and I , showing how symmetry or geometrical change in cage structure can influence motional behavior cluster. Inside cage, primary cerium sites identified along a belt...

Additions of adamantylidene (Ad) to M3 N@Ih -C80 (M=Sc, Lu) and Sc3 N@D5h have been accomplished by photochemical reactions with 2-adamantyl-2,3'-[3H]-diazirine (1). In , the addition led rupture [6,6]- or [5,6]-bonds Ih cage, forming [6,6]-open fulleroid as major isomer [5,6]-open minor isomer. also proceeded regioselectively yield three isomeric Ad mono-adducts, despite fact that there are nine types C-C bonds in D5h cage. The molecular structures seven including positions encaged...

Alkylated single-walled carbon nanotubes (SWNTs) have been thermally treated to determine the influence of substituents and degree functionalization on their thermal stability photoluminescence (PL) properties. SWNTs were prepared by treating with sodium naphthalenide alkyl bromide. The defunctionalization alkylated was monitored absorption Raman spectra. Selective recovery characteristic radial breathing mode peaks observed during treatment, which indicates that decreases increases in SWNT...

An open-cage fullerene bearing an eight-membered ring orifice has been synthesized in one pot by the reaction of C60 with propargylic phosphate presence CuCl. The cascade involves transformation to 1,3-dienyl phosphate, which enables [4 + 2] cycloaddition form cyclohexene-annulated intermediate, and subsequent intramolecular syn-elimination phosphodiester affords cyclohexadiene-annulated derivative as precursor for fullerene.

Indantrione 1,2-dioxime (1) afforded crystals solvated by different species of alcohols and in stoichiometries. Among those, three pairs polymorphic forms, which are the same solvent stoichiometry, were obtained. The crystal structures those polymorphs, formulated as α- β-1·MeOH, β-1·1/2MeOH, β-1·EtOH, elucidated along with that 1·i-PrOH. common building block is a centrosymmetric planar dimer linked bifurcated hydrogen bonding. further assembled through alcohol molecules to form tapelike...

Location recognition at the molecular scale provides valuable information about nature of functional materials. This study presents a novel location sensing approach based on an endohedral metallofullerene, Ce@C82, using its anisotropic magnetic properties, which lead to temperature-dependent paramagnetic shifts in 1H NMR spectra. Five site-isomers Ce@C82CH2-3,5-C6H3Me2 were synthesized demonstrate spatial ability Ce@C82. Single-crystal structures, absorption spectra, and density theory...

The effect of ultrasonic irradiation on the optical properties single-walled carbon nanotubes (SWNTs) was investigated. Upon sonication in D2O presence sodium dodecylbenzene sulfonate (SDBS) under air, red-shifted photoluminescence (PL) peaks at ∼1043 and ∼1118 nm were observed from aqueous suspensions (6,4) (6,5)SWNTs, accompanied by a decrease intensity intrinsic PL peaks. with SDBS an Ar atmosphere, rate spectral change increased time new emerged 1043, 1118, 1221 nm. Meanwhile, upon...

White phosphorescent light emission from polymer light-emitting devices (PLEDs) has been demonstrated. To fabricate the white-emitting PLED, blue (BPP) and red (RPP) were used for emissive layer, color was tuned by controlling concentration ratio of BPP to RPP. The external quantum efficiency with CIE coordinates (0.34, 0.36), 6.0% at luminance 100 cd/m/sup 2/. investigate mechanism in its photoluminescence spectrum transient decay measured. These experimental measurements indicate that...