Simultaneous Ring Contraction and Expansion Reaction: Electrosynthesis of Heterocycle-Fused Fulleroids and Photovoltaic Application.

Simultaneous electrochemical ring contraction and expansion reactions remain unexplored to date. Herein, the reductive electrosynthesis of heterocycle-fused fulleroids from fullerotetrahydropyridazines and electrophiles in the presence of a trace amount of oxygen has been achieved with concurrent ring contraction and ring expansion. When trifluoroacetic acid and alkyl bromides are employed as electrophiles, heterocycle-fused fulleroids with a 1,1,2,6-configuration are regioselectively formed. In contrast, heterocycle-fused fulleroids with a 1,1,4,6-configuration are regioselectively produced as two separable stereoisomers if phthaloyl chloride is used as the electrophile. The reaction proceeds through multiple steps of electroreduction, heterocycle ring-opening, oxygen oxidation, heterocycle contraction, fullerene cage expansion, and nucleophilic addition. The structures of these fulleroids have been determined by spectroscopic data and single-crystal X-ray diffraction analyses. The observed high regioselectivities have been rationalized by theoretical calculations. Representative fulleroids have been applied in organic solar cells as the third component and exhibit good performance.

Palladium-Catalyzed Three-Component 1,4-Alkoxyarylation Reaction of [60]Fullerene.

The palladium-catalyzed three-component alkoxyarylation reaction of [60]fullerene with primary/secondary alcohols and aryl iodides generates a series of 1,4-(alkoxy)(aryl)[60]fullerene derivatives. Plausible reaction pathways for the formation of 1,4-(alkoxy)(aryl)[60]fullerenes are proposed. In addition, the electrochemical properties of the synthesized 1,4-alkoxyarylation adducts are investigated.

Alternative Access to Cyclopentafullerenes through the Reaction of [60]Fullerene with Aldehydes and Secondary Amines.

A series of cyclopentafullerenes have been synthesized in high stereoselectivity by the thermal reaction of [60]fullerene with aldehydes and secondary amines. Both α,ß-unsaturated aldehydes and saturated aldehydes can be utilized to synthesize cyclopentafullerenes as the cis isomers. The possible reaction mechanisms for the formation of cyclopentafullerenes are proposed on the basis of the experimental results.

Synthesis of [60]Fullerene-Fused Lactones via Carboxylic Acid Group-Directed C-H Bond Activation and Further Retro Baeyer-Villiger Reaction.

An efficient palladium-catalyzed reaction of [60]fullerene with benzoic acids via carboxylic acid group-directed C-H bond activation is achieved. The obtained [60]fullerene-fused lactones can undergo a retro Baeyer-Villiger reaction to provide [60]fullerene-fused ketones via apparent reduction in the presence of triflic acid. A representative ketone product obtained by the reduction reaction can be employed as an overcoating layer for the electron-transporting layer in an n-type perovskite solar cell.

Unexpected and divergent mechanosynthesis of furanoid-bridged fullerene dimers C120O and C120O2.

An unexpected, divergent and efficient approach toward furanoid-bridged fullerene dimers C120O and C120O2 was established under different solvent-free ball-milling conditions by simply using pristine C60 as the starting material, water as the oxygen source and FeCl3 as the mediator. The structures of C120O and C120O2 were unambiguously established by single-crystal X-ray crystallography. A plausible reaction mechanism is proposed on the basis of control experiments. Furthermore, C120O2 has been applied in organic solar cells as the third component and exhibits good performance.

Interface Passivation of a Pyridine-Based Bifunctional Molecule for Inverted Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells (PSCs) have recently been demonstrated to be promising renewable harvesters because of their prominent photovoltaic power conversion efficiency (PCE), although their stability and efficiency still have not reached commercial criteria. Trouble-oriented analyses showcase that defect reduction among the grain boundaries and interfaces in the prepared perovskite polycrystalline films is a practical strategy, which has prompted researchers to develop functional molecules for interface passivation. Herein, the pyridine-based bifunctional molecule dimethylpyridine-3,5-dicarboxylate (DPDC) was employed as the interface between the electron-transport layer and perovskite layer, which achieved a champion PCE of 21.37% for an inverted MAPbI3-based PSC, which was greater than 18.64% for the control device. The mechanistic studies indicated that the significantly improved performance was mainly attributed to the remarkably enhanced fill factor with a value greater than 83%, which was primarily due to the nonradiative recombination suppression offered by the passivation effect of DPDC. Moreover, the promoted carrier mobility together with the enlarged crystal size contributed to a higher short-circuit current density. In addition, an increase in the open-circuit voltage was also observed in the DPDC-treated PSC, which benefited from the improved work function for reducing the energy loss during carrier transport. Furthermore, the DPDC-treated PSC showed substantially enhanced stability, with an over 80% retention rate of its initial PCE value over 300 h even at a 60% relative humidity level, which was attributed to the hydrophobic nature of the DPDC molecule and effective defect passivation. This work is expected not only to serve as an effective strategy for using a pyridine-based bifunctional molecule to passivate perovskite interfaces to enhance photovoltaic performance but also to shed light on the interface passivation mechanism.

Visible-Light-Promoted C4-Selective Phosphorylation of Pyridine and Quinoline Derivatives.

The visible-light-promoted C4-selective phosphorylation of unprefunctionalized pyridine and quinoline derivatives has been accomplished. This Minisci-type protocol provides highly regioselective access to C4-phosphorylation products with good functional group tolerance and moderate to good yields via cross-dehydrogenation coupling under mild conditions. Mechanistic studies have shown that the C4-phosphorylation products are obtained via a radical pathway.

Electrosynthesis of buckyballs with fused-ring systems from PCBM and its analogue.

[6,6]-Phenyl-C61-butyric acid methyl ester (PCBM), a star molecule in the fullerene field, has found wide applications in materials science. Herein, electrosynthesis of buckyballs with fused-ring systems has been achieved through radical α-C-H functionalization of the side-chain ester for both PCBM and its analogue, [6,6]-phenyl-C61-propionic acid methyl ester (PCPM), in the presence of a trace amount of oxygen. Two classes of buckyballs with fused bi- and tricyclic carbocycles have been electrochemically synthesized. Furthermore, an unknown type of a bisfulleroid with two tethered [6,6]-open orifices can also be efficiently generated from PCPM. All three types of products have been confirmed by single-crystal X-ray crystallography. A representative intramolecularly annulated isomer of PCBM has been applied as an additive to inverted planar perovskite solar cells and boosted a significant enhancement of power conversion efficiency from 15.83% to 17.67%.

Electrosynthesis of Decorated Basket Molecules: [60]Fullerene-Fused 12-Membered Macrolactones.

The electrosynthesis of decorated basket molecules, that is, [60]fullerene-fused 12-membered macrolactones, has been achieved efficiently for the first time by the electrochemical reduction of [60]fullerene-fused 6-membered lactones and subsequent ring expansion with 1,2-bis(1-bromoalkyl)benzenes. The observed isomeric distributions of the obtained macrolactones are elucidated by theoretical calculations. The product structures have been firmly established by single-crystal X-ray analyses.

Retro Baeyer-Villiger reaction: thermal conversion of the [60]fullerene-fused lactones to ketones.

The conversion of the [60]fullerene-fused lactones to ketones with triflic anhydride as an unusual reductant under aerobic conditions has been achieved in excellent yields. The present thermal retro Baeyer-Villiger reaction from lactones to ketones has no precedents. In addition, the unique ring-opened peroxy [60]fullerene derivatives can be obtained by the electrochemical reactions of the synthesized [60]fullerene-fused ketones.

A copper-promoted synthesis of epoxy-bridged [60]fullerene-fused lactones and further derivatization.

A facile copper-promoted decarboxylative annulation of [60]fullerene (C60) with two identical α-oxocarboxylic acids via an unprecedented cascade addition pathway has been exploited to synthesize the unique epoxy-bridged C60-fused lactones for the first time. Further transformations into the rare epoxy-bridged C60-fused hemiacetals and bicyclic-fused 1,2,3,4-adducts as well as application in a perovskite solar cell device of the obtained products have also been demonstrated. The structures of the epoxy-bridged C60-fused lactones and derived reductive products have been unequivocally established by single-crystal X-ray crystallography. Plausible reaction mechanisms leading to the observed products are proposed.

Unexpected Diels-Alder reaction of [60]fullerene with electron-deficient ferrocenes as cyclopentadiene surrogates.

The unexpected Diels-Alder reaction of [60]fullerene (C60) with ferrocenes bearing electron-withdrawing groups as cyclopentadiene surrogates has been developed to selectively afford single isomers of [2 + 4] cycloadducts of C60. Mechanistic studies indicate that cyclopentadienes are in situ generated from electron-deficient ferrocenes in the presence of an oxidant and an acid, followed by [2 + 4] cycloadditions with dienophiles. A Michael addition reaction using a Grignard reagent has been utilized to transform the Diels-Alder adducts of C60 into more stable fullerene derivatives.

Cu(I)-Catalyzed Synthesis of [60]Fullerene-Fused Lactams and Further Electrochemical Functionalization.

A novel and efficient Cu(I)-catalyzed radical heteroannulation reaction of [60]fullerene (C60) with α-bromo acetamides has been disclosed for the direct synthesis of diverse C60-fused lactams. Furthermore, the formed C60-fused lactams can be served as a versatile platform for further electrochemical functionalization to prepare 1,2-, 1,4-, 1,2,3,16-, and 1,4,9,25-adducts of C60. In addition, a representative fullerene product has been applied as an overcoating layer of the electron-transporting layer in n-type perovskite solar cell.

A retro Baeyer-Villiger reaction: electrochemical reduction of [60]fullerene-fused lactones to [60]fullerene-fused ketones.

A highly efficient electrochemical reduction of [60]fullerene-fused lactones to [60]fullerene-fused ketones, a formal process of retro Baeyer-Villiger reaction, has been achieved for the first time. The electrochemically generated dianionic [60]fullerene-fused lactones can be transformed into [60]fullerene-fused ketones in the presence of acetic acid in 85-91% yields. Control experiments have been performed to elucidate the reaction mechanism. The products have been characterized with spectroscopic data and single-crystal X-ray analysis. Moreover, the electrochemical properties have also been investigated.

Electrochemical Benzylation of [60]Fullerene-Fused Lactones: Unexpected Formation of Ring-Opened Adducts and Their Photovoltaic Performance.

Electrochemical benzylation of [60]fullerene-fused lactones with different motifs unexpectedly affords three types of ring-opened benzylated adducts under different conditions. Both [60]fullerene-fused δ- and γ-lactones can be benzylated to generate ring-opened mono- and bis-benzylated adducts in good yields. In addition, representative fullerene products have been applied as efficient electron-transport materials in perovskite solar cells.