Ferric Perchlorate-Mediated Synthesis of 1,2-Fullerenols C₆₀(OCOR)(OH)

1,2-Fullerenols C₆₀(OCOR)­(OH) have been facilely synthesized via the one-step reaction of [60]­fullerene with acid chlorides promoted by ferric perchlorate. A possible reaction mechanism for the product formation is proposed

Synthesis of Ortho Acid Ester-Type 1,3-Dioxolanofullerenes: Radical Reaction of [60]Fullerene with Halocarboxylic Acids Promoted by Lead(IV) Acetate

A lead­(IV) acetate-promoted radical reaction of [60]­fullerene with halocarboxylic acids has been exploited to synthesize rare ortho acid ester-type 1,3-dioxolanofullerenes, the hydroxyl group of which can be further transformed to an ester or ether group. Intriguingly, an ortho acid ester-type 1,3-dioxolanofullerene can also be converted to a 1,4-dioxanonofullerene in the presence of a base or manipulated to another ortho acid ester-type 1,3-dioxolanofullerene by reaction with a stronger halocarboxylic acid. Moreover, two possible reaction pathways leading to the observed products are also proposed

Fullerenyl Boronic Esters: Ferric Perchlorate-Mediated Synthesis and Functionalization

Fullerenyl boronic esters have been prepared by a ferric perchlorate-promoted reaction of [60]fullerene with various arylboronic acids. The obtained fullerenyl boronic esters could undergo further functionalization with diols to afford C₆₀-fused dioxane/dioxepane derivatives. A possible reaction mechanism for the formation of fullerenyl boronic esters has been proposed

Synthesis of Fullerene-Fused Dioxanes/Dioxepanes: Ferric Perchlorate-Mediated One-Step Reaction of [60]Fullerene with Diols

The facile one-step reaction of [60]­fullerene with various diols in the presence of ferric perchlorate afforded a series of rare fullerene-fused dioxanes/dioxepanes. Nevertheless, the reaction of [60]­fullerene with diethylene glycol, triethylene glycol, and tripropylene glycol promoted by ferric perchlorate unexpectedly generated fullerene-fused dioxanes instead of the anticipated fullerene-fused crown ethers. A plausible reaction mechanism is proposed to explain the formation of fullerene-fused dioxane/dioxepane products

BF₃·Et₂O‑Catalyzed Formal [3 + 2] Reaction of Aziridinofullerenes with Carbonyl Compounds

The BF₃·Et₂O-catalyzed formal [3 + 2] reaction of aziridinofullerenes with various carbonyl compounds for the easy preparation of fullerooxazolidines has been developed. Moreover, the reaction of aziridinofullerene with ethyl formate affords the simplest fullerooxazole without substituent

Synthesis, characterization and luminescent properties of three-coordinate copper(I) halide complexes containing 2-(diphenylphosphino)biphenyl

<p>Highly emissive three-coordinate copper halide complexes with a bidentate phosphine ligand have attracted attention. Here, a series of three-coordinate mono- and dinuclear copper halide complexes, [CuI(dpbp)₂] (<b>1</b>) and [CuX(dpbp)]₂ (dpbp = 2-(diphenylphosphino)biphenyl, X = Br (<b>2</b>), Cl (<b>3</b>)), were synthesized, and their molecular structures and photophysical properties were investigated. In the solid state, these complexes exhibit green photoluminescence with microsecond lifetimes (<i>λ</i>_max = 515–538 nm; <i>τ</i> = 11.8–19.1 <i>μ</i>s) at 298 K. The emission of the complexes originates from the (<i>σ</i> + X) → <i>π</i>* transition. All three complexes displayed good thermal stability.</p

Cu(OAc)₂‑Mediated Reaction of [60]Fullerene with Aldehydes and Primary Amines for the Synthesis of Fulleropyrrolines

The facile one-step reaction of [60]­fullerene with aldehydes and primary amines in the presence of cheap and easily available Cu­(OAc)₂·H₂O afforded a series of new types of fulleropyrrolines with trisubstituted CC bonds in good to excellent yields, which would be difficult to prepare by known methods. The formed fulleropyrroline under the assistance of Pd­(OAc)₂ and CuCl₂·2H₂O could be further converted to 1-fulleropyrrolidine by the chlorohydroxylation reaction of CC bond. Subsequent elimination reaction of 1-fulleropyrrolidine with the aid of TsOH·H₂O generated the scarce 1-fulleropyrroline derivative

DMAP-Mediated Synthesis of Fulleropyrrolines: Reaction of [60]Fullerene with Aromatic Aldehydes and Arylmethanamines in the Absence or Presence of Manganese(III) Acetate

A series of scarce fulleropyrrolines were synthesized via DMAP-mediated one-step reaction of [60]­fullerene with commercially inexpensive aromatic aldehydes and arylmethanamines in the absence or presence of manganese­(III) acetate. In the case of aminodiphenylmethane, novel 2,5,5-trisubstituted fulleropyrrolines could be easily obtained without the addition of manganese­(III) acetate. As for arylmethanamines without α-substitutions, the addition of manganese­(III) acetate was required to suppress the formation of fulleropyrrolidines, in order to generate the desired 2,5-disubstituted fulleropyrrolines. Two tautomers were produced as expected when different aryl groups (Ar¹ ≠ Ar²) from aromatic aldehydes and arylmethanamines were employed in the synthesis. A plausible reaction mechanism for the formation of fulleropyrrolines is proposed

Synthesis, characterization and luminescent properties of copper(I) halide complexes containing biphenyl bidentate phosphine ligand

<p>Copper(I) halide complexes having thermally activated delayed fluorescence (TADF) and phosphorescence have attracted much attention. Here, a series of four-coordinate dinuclear copper(I) halide complexes, [CuX(bpbp<b>)</b>]₂ (bpb<i>p</i> = 2,2′-bis(diphenylphosphino)biphenyl, X = I (<b>1</b>), Br (<b>2</b>) and Cl (<b>3</b>)), were synthesized, and their molecular structures and photophysical properties were investigated. The structural analysis reveals that two copper(I) centers are bridged by two halogen ligands to form a dinuclear structure with a four-membered Cu₂X₂ ring. These complexes exhibit yellow to blue emission in the solid state at room temperature and have peak emission wavelengths at 575–487 nm with microsecond lifetimes (<i>τ</i> = 6.2–19.8 μs) and low emission quantum yields (<0.01%). The emissions of <b>1</b>–<b>3</b> originate from MLCT, XLCT, and IL (intraligand) transitions. Three complexes displayed good thermal stability.</p

Synthesis of 2‑Aryl-5-alkyl-fulleropyrrolidines: Metal-Free-Mediated Reaction of [60]Fullerene with Aromatic Aldehydes and Inactive Primary Amines

The metal-free-mediated thermal reaction of [60]­fullerene with aromatic aldehydes and inactive primary amines bearing electron-donating groups at the α-position afforded a series of 2-aryl-5-alkyl-fulleropyrrolidines, including the scarce 2-aryl-5-benzyl-fulleropyrrolidines as a mixture of <i>cis</i> and <i>trans</i> isomers. With rare exceptions, the mixture of <i>cis</i> and <i>trans</i> isomers could be easily isolated by column chromatography, with a preference of <i>cis</i> isomers as major products. A plausible mechanism for the formation of fulleropyrrolidines is also proposed