Conjugated Molecular Nanotubes Mirzaei, Saber; Castro, Edison; Hernández Sánchez, Raúl
Chemistry : a European journal,
June 16, 2021, Letnik:
27, Številka:
34
Journal Article
Recenzirano
Molecular compounds with permanent tubular architectures displaying radial π‐conjugation are exceedingly rare. Their radial and axial delocalization presents them with unique optical and electronic ...properties, such as remarkable tuning of their Stokes shifts, and redox switching between global and local aromaticity. Although these tubular compounds display large internal void spaces, these attributes have not been extensively explored, thus presenting future opportunities in the development of materials. By using cutting‐edge synthetic methodologies to bend aromatic surfaces, large opportunities in synthesis, property discovery, and applications are expected in new members of this family of conjugated molecular nanotubes.
Synthetic efforts to bend aromatic surfaces have had a remarkable evolution during the last dozen years. Conjugated nanorings and nanobelts are among the most well‐known examples. However, this progress has also led to the synthesis of molecular compounds with permanent tubular shapes with radial and axial π surfaces, which are the highlight of this Minireview.
Remarkable recent advances on Au25(SR)18 nanoclusters have led to significant applications in catalysis, sensing, and magnetism. However, the existing synthetic routes are complicated, particularly ...for the water-soluble Au25(SG)18 nanoclusters. Here, we report a single-step concentration and temperature-controlled method for rapid synthesis of the Au25(SG)18 nanoclusters in as little as 2 h without the need for low-temperature reaction or even stirring. A systematic time-based investigation was carried out to study the effects of volume, concentration, and temperature on the synthesis of these nanoclusters. Further, we discovered for the first time that the Au25(SG)18 nanoclusters exhibit excellent photothermal activities in achieving 100% cell death for MDA-MB-231 breast cancer cells at a power of 10 W/cm2 using an 808 nm laser source, demonstrating applications toward photothermal therapy.
Two cove‐edge graphene nanoribbons hPDI2‐Pyr‐hPDI2 (1) and hPDI3‐Pyr‐hPDI3 (2) are used as efficient electron‐transporting materials (ETMs) in inverted planar perovskite solar cells (PSCs). Devices ...based on the new graphene nanoribbons exhibit maximum power‐conversion efficiencies (PCEs) of 15.6 % and 16.5 % for 1 and 2, respectively, while a maximum PCE of 14.9 % is achieved with devices based on 6,6‐phenyl‐C61‐butyric acid methyl ester (PC61BM). The interfacial effects induced by these new materials are studied using photoluminescence (PL), and we find that 1 and 2 act as efficient electron‐extraction materials. Additionally, compared with PC61BM, these new materials are more hydrophobic and have slightly higher LUMO energy levels, thus providing better device performance and higher device stability.
Blue (nano)ribbon solar cells: Two electron‐deficient graphene nanoribbons are used as the electron‐transporting materials (ETMs) in inverted perovskite solar cells (PSCs). The nanoribbons provide improved performance over the commonly used PC61BM. The most important benefits are the improved PCE (>10 % over PC61BM) and improved device lifetime owing to the hydrophobic nature of the solubilizing chains on the ribbons.
Three compounds (1, 2, and 3) previously reported to inhibit HIV-1 replication and/or in vitro activity of reverse transcriptase were studied, but only fullerene derivatives 1 and 2 showed strong ...antiviral activity on the replication of HIV-1 in human CD4(+) T cells. However, these compounds did not inhibit infection by single-round infection vesicular stomatitis virus glycoprotein G (VSV-G)-pseudotyped viruses, indicating no effect on the early steps of the viral life cycle. In contrast, analysis of single-round infection VSV-G-pseudotyped HIV-1 produced in the presence of compound 1 or 2 showed a complete lack of infectivity in human CD4(+) T cells, suggesting that the late stages of the HIV-1 life cycle were affected. Quantification of virion-associated viral RNA and p24 indicates that RNA packaging and viral production were unremarkable in these viruses. However, Gag and Gag-Pol processing was affected, as evidenced by immunoblot analysis with an anti-p24 antibody and the measurement of virion-associated reverse transcriptase activity, ratifying the effect of the fullerene derivatives on virion maturation of the HIV-1 life cycle. Surprisingly, fullerenes 1 and 2 did not inhibit HIV-1 protease in an in vitro assay at the doses that potently blocked viral infectivity, suggesting a protease-independent mechanism of action. Highlighting the potential therapeutic relevance of fullerene derivatives, these compounds block infection by HIV-1 resistant to protease and maturation inhibitors.
An ultimate goal in carbon nanoscience is to decipher formation mechanisms of highly ordered systems. Here, we disclose chemical processes that result in formation of high-symmetry clusterfullerenes, ...which attract interest for use in applications that span biomedicine to molecular electronics. The conversion of doped graphite into a C
cage is shown to occur through bottom-up self-assembly reactions. Unlike conventional forms of fullerene, the iconic Buckminsterfullerene cage, I
-C
, is entirely avoided in the bottom-up formation mechanism to afford synthesis of group 3-based metallic nitride clusterfullerenes. The effects of structural motifs and cluster-cage interactions on formation of compounds in the solvent-extractable C
-C
region are determined by in situ studies of defined clusterfullerenes under typical synthetic conditions. This work establishes the molecular origin and mechanism that underlie formation of unique carbon cage materials, which may be used as a benchmark to guide future nanocarbon explorations.
We describe a solid state material created from the reaction of Ni9Te6(PEt3)8 and Lu3N@C80. The resulting superatomic crystal, Ni12Te12(PEt3)82(Lu3N@C80)2, contains dimers of Lu3N@C80 that form upon ...reduction of the fullerene through a single C−C bond at the triple hexagon junctions. The encapsulated Lu3N cluster displays an unprecedented orientation that is collinear and coplanar with the intercage carbon bond. Density functional theory calculations rationalize this unique bonding and relative orientation of the Lu3N clusters. Our structural and theoretical results provide new insights into the effect that the M3N cluster species has on the dimerization process of endohedral fullerenes.
Endohedral fullerene dimers were formed upon reaction with a nickel telluride molecular cluster. The resulting solid‐state material assembled into a superatomic relative of the Rb2O2 structure‐type. The single‐bonded endohedral fullerene dimer features a unique orientation of the encapsulated cluster.
Absorption and redox properties of seven decakis(phenylthio)corannulene derivatives 3a–3g lead to a model for estimating material properties in persulfurated aromatic compounds. The same series is ...evaluated for performance in bulk heterojunction and perovskite photovoltaic devices.
Absorption and redox properties of seven decakis(phenylthio)corannulene derivatives lead to a model for estimating material properties in persulfurated aromatic compounds.
The synthesis, characterization, and incorporation of open-cage 60fullerene derivatives as electron-transporting materials (ETMs) in perovskite solar cells (PSCs) with an inverted planar (p-i-n) ...structure is reported. Following optical and electrochemical characterization of the open-cage fullerenes
-
, p-i-n PSCs with a indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS)/perovskite/fullerene/Ag structure were prepared. The devices obtained from
-
exhibit competitive power conversion efficiencies (PCEs) and improved open-circuit voltage (
) values (>1.0 V) in comparison to a reference cell based on phenyl-C
-butyric-acid methyl-ester (PC
BM). These results are rationalized in terms of a) the higher passivation ability of the open-cage fullerenes with respect to the other fullerenes, and b) a good overlap between the highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) levels of
-
and the conduction band of the perovskite.
Fullerene derivatives with hydrophilic substituents have been shown to exhibit a range of biological activities, including antiviral ones. For a long time, the anti-HIV activity of fullerene ...derivatives was believed to be due to their binding into the hydrophobic pocket of HIV-1 protease, thereby blocking its activity. Recent work, however, brought new evidence of a novel, protease-independent mechanism of fullerene derivatives' action. We studied in more detail the mechanism of the anti-HIV-1 activity of
,
-dimethyl70fulleropyrrolidinium iodide fullerene derivatives. By using a combination of
and cell-based approaches, we showed that these C
derivatives inhibited neither HIV-1 protease nor HIV-1 maturation. Instead, our data indicate effects of fullerene C
derivatives on viral genomic RNA packaging and HIV-1 cDNA synthesis during reverse transcription-without impairing reverse transcriptase activity though. Molecularly, this could be explained by a strong binding affinity of these fullerene derivatives to HIV-1 nucleocapsid domain, preventing its proper interaction with viral genomic RNA, thereby blocking reverse transcription and HIV-1 infectivity. Moreover, the fullerene derivatives' oxidative activity and fluorescence quenching, which could be one of the reasons for the inconsistency among reported anti-HIV-1 mechanisms, are discussed herein.
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