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The ring-opening reaction of aromatic molecules is a significant and critical process for the construction of carbon-based and related functional materials with desired structures and properties. However, direct observation and control of such a process at a molecular level remains a challenge. Here, we employed the octahedral voids in endohedral metallofullerene (EMF) crystals as nanoreactors to accommodate aromatic m-xylene molecules and regulate the ring-opening reaction of guest m-xylene by applying a high pressure. We found that the ring-opening reaction of m-xylenes strongly depends on the degree of charge transfer between m-xylene and EMF, which can be tuned by varying the electronegativity of the carbon cages with different endohedral metals. A positive relationship between the electronegativity of fullerenes and the reactivity of m-xylene was revealed. This work demonstrates the potential of tuning the ring-opening reaction of aromatic molecules by charge transfer and manipulates the reaction at a molecule level, providing new insights into the synthesis of carbon materials and fullerene derivatives. [ABSTRACT FROM AUTHOR]

Fullerene derivatives are extensively employed in inverted perovskite solar cells due to their excellent electron extraction capabilities. However, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) agglomerates easily in solution and exhibits a relatively low ionization barrier, increasing charge recombination losses and charge accumulation in the interface. Here, tetramethylthiuram disulfide (TMDS) is introduced into the PCBM solution to induce the formation of reducing sulfur radicals through UV light irradiation, allowing for n doping of the PCBM material. The resulting modified PCBM layer exhibits enhanced conductivity and electron mobility, significantly suppressing charge recombination. As a result, the resulting devices incorporating TMDS achieve a champion efficiency of 26.10% (certified 25.39%) and 24.06% at a larger area (1.0 cm2) with negligible hysteresis. More importantly, the optimized devices retain 95% and 90% of their initial efficiency after 1090 h under damp heat testing (85 °C and 85% relative humidity) and after 1271 h under maximum power point-tracking conditions, respectively. Fullerene derivatives tend to increase charge recombination losses and charge accumulation at the interface in inverted perovskite solar cells. Here, authors introduce tetramethylthiuram disulfide to induce formation of sulfur radicals for n-doping, achieving efficiency of 26.1% in stable devices. [ABSTRACT FROM AUTHOR]

Among C60's diverse functionalities, its potential application in CO2 sequestration has gained increasing interest. However, the processes involved are sensitive to the molecule's electronic structure, aspects of which remain debated and require greater precision. To address this, we performed structural optimization of fullerene C60 using the QM MP2/6–31G* method. The nonplanarity of the optimized icosahedron is characterized by two types of dihedral angles: 138° and 143°. The 120 dihedrals of 138° occur between two hexagons intersecting at C–C bonds of 1.42 Å, while the 60 dihedrals of 143° are observed between hexagons and pentagons at C–C bonds of 1.47 Å. NBO analysis reveals less pyramidal sp1.78 hybridization for carbons at the 1.42 Å bonds and more pyramidal sp2.13 hybridization for the 1.47 Å bonds. Electrostatic potential charges range from −0.04 a.u. to 0.04 a.u. on the carbon atoms. Second-order perturbation analysis indicates that delocalization interactions in the C–C bonds of 1.42 Å (143.70 kcal/mol) and 1.47 Å (34.98 kcal/mol) are 22% and 38% higher, respectively, than those in benzene. MP2/Def2SVP calculations yield a correlation energy of 13.49 kcal/mol per electron for C60, slightly higher than the 11.68 kcal/mol for benzene. However, the results from HOMO-LUMO calculations should be interpreted with caution. This study may assist in the rational design of fullerene C60 derivatives for CO2 reduction systems. [ABSTRACT FROM AUTHOR]

With excellent biocompatibility, a narrow bandgap, and long thermal carrier lifetime, tin‐based perovskite solar cells (TPSCs) are promising within the solar technology. The fullerene derivative indene‐C60 bisadduct (ICBA) is recognized as the most efficient electron‐transport material for TPSCs, thanks to its suitable band structure. Nevertheless, the limited electron transport capability and susceptibility to moisture penetration of ICBA have hindered the progress of TPSCs. Herein, the study proposes a new hydrophobic electron‐transport layer (ETL) comprising a surface‐anchored non‐fullerene n‐type semiconducting polymer layer, poly (naphthalene diimide‐alt‐dithiophenebezothiadiazole) (PNDI‐BT), in conjunction with ICBA. PNDI‐BT exhibits high electron mobilities, a fitting band structure, robust interaction with Sn‐based perovskites, and exceptional moisture resistance, effectively addressing the shortcomings of ICBA. Consequently, this innovative hydrophobic ETL of PNDI‐BT/ICBA enhances electron transport and protects Sn‐based perovskites from moisture. As a result, the inverted TPSCs with the new hydrophobic ETL achieve an impressive efficiency of 13.90%, surpassing TPSCs with the ICBA layer (12.75%). Moreover, even after 1000 h of storage in ambient atmosphere, the encapsulated TPSC maintains a remarkable 81% of its initial efficiency. This comprehensive study seamlessly integrates the synthesis of non‐fullerene n‐type semiconducting polymer and device fabrication, providing valuable insights into designing cutting‐edge ETL structure for inverted TPSCs. [ABSTRACT FROM AUTHOR]

Wenjia Hou,1,2,* Lan Shen,1,* Yimin Zhu,1 Xuanjia Wang,1 Tianyu Du,1 Fang Yang,1 Yabin Zhu1 1Health Science Center, Ningbo University, Ningbo, 315211, People’s Republic of China; 2State Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai, 200438, People’s Republic of China*These authors contributed equally to this workCorrespondence: Wenjia Hou; Yabin Zhu, Email houwenjia@nbu.edu.cn; zhuyabin@nbu.edu.cnAbstract: Fullerenes hold tremendous potential as alternatives to conventional chemotherapy or radiotherapy for tumor treatment due to their abilities to photodynamically kill tumor cells, destroy the tumor vasculature, inhibit tumor metastasis and activate anti-tumor immune responses, while protecting normal tissue through antioxidative effects. The symmetrical hollow molecular structures of fullerenes with abundant C=C bonds allow versatile chemical modification with diverse functional groups, metal clusters and biomacromolecules to synthesize a wide range of fullerene derivatives with increased water solubility, improved biocompatibility, enhanced photodynamic properties and stronger targeting abilities. This review introduces the anti-tumor mechanisms of fullerenes and summarizes the most recent works on the functionalization of fullerenes and the application of fullerene derivatives in tumor treatment. This review aims to serve as a valuable reference for further development and clinical application of anti-tumor fullerene derivatives. Keywords: fullerene derivatives, tumor treatment, photodynamic treatment, metastasis inhibition, tumor vasculature, cellular immunity

Comprehensive Summary: In recent years, there has been a shift towards using non‐fullerene electron acceptors in organic solar cells (OSCs) as a replacement for fullerene derivatives. This change requires polymer donors that possess compatible physical properties, such as absorption range, HOMO energy level, miscibility, and crystallinity. Moreover, the high cost and poor batch‐to‐batch reproducibility of polymer donors also hinder future large‐scale manufacturing. These emphasize the need to explore alternative types of polymer donors. The imide‐functionalized building units possess several key attributes that make their polymers highly promising for non‐fullerene OSCs. These attributes include ease of synthesis, strong electron‐withdrawing ability, rigid and co‐planar structure, and the ability to easily tune solubility through imide side chains. In this review, we summarized the synthetic routes of imide building units, and the structural evolution of imide‐functionalized polymer donors by focusing on the effects of polymer structure on their physical, optoelectronic, and photovoltaic properties. We hope that this mini‐review will serve as a catalyst for future research on imide‐functionalized polymers toward high‐performance, cost‐effective, and durable organic solar cells (OSCs). [ABSTRACT FROM AUTHOR]

Comprehensive Summary: In recent years, there has been a shift towards using non‐fullerene electron acceptors in organic solar cells (OSCs) as a replacement for fullerene derivatives. This change requires polymer donors that possess compatible physical properties, such as absorption range, HOMO energy level, miscibility, and crystallinity. Moreover, the high cost and poor batch‐to‐batch reproducibility of polymer donors also hinder future large‐scale manufacturing. These emphasize the need to explore alternative types of polymer donors. The imide‐functionalized building units possess several key attributes that make their polymers highly promising for non‐fullerene OSCs. These attributes include ease of synthesis, strong electron‐withdrawing ability, rigid and co‐planar structure, and the ability to easily tune solubility through imide side chains. In this review, we summarized the synthetic routes of imide building units, and the structural evolution of imide‐functionalized polymer donors by focusing on the effects of polymer structure on their physical, optoelectronic, and photovoltaic properties. We hope that this mini‐review will serve as a catalyst for future research on imide‐functionalized polymers toward high‐performance, cost‐effective, and durable organic solar cells (OSCs). [ABSTRACT FROM AUTHOR]

Fullerenes and their derivatives have great potential for use as materials for medicine and biology. Fullerenes can enter into various reactions due to the presence of double bonds in their structure; it has also been repeatedly noted in the literature that the molecules have antiradical activity, biocompatibility, the ability to pass through biobarriers and immobilize various active molecules. In this work, a water-soluble adduct of C60 fullerene with glycine was synthesized, its physicochemical properties, biocompatibility were studied, and a protective effects toward collagen photodegradation as well as in the model reaction of human serum albumin glycation was shown. [ABSTRACT FROM AUTHOR]

Herein, we report on the family of fullerene derivatives F2-F6 as electron transport materials (ETMs) in inverted perovskite solar cells (PSCs). According to the results, F2 and F4 have power conversion efficiencies (PCE) of 17.2% and 16.7%, respectively, which indicates better performance than conventional ETM (PC61BM). Utilizing infrared scattering scanning near-field optical microscopy (IR s-SNOM), we ascertained that F2 and F4 demonstrate exceptional uniformity and are devoid of defects. This characteristic contributes to a reduction in trap density and charge recombination in PSCs, ultimately enhancing device efficiency and mitigating hysteresis. Above all, F2 showed no signs of deterioration when the PSCs were exposed to 45 ± 5% relative humidity for 1000 h. Our research provides an innovative viewpoint on how to create novel fullerene compounds that enhance efficiency and stability of PSCs. [ABSTRACT FROM AUTHOR]

Natural photosynthesis holds great potential to generate clean electricity from solar energy. In order to utilize this process for power generation, it is necessary to rewire photosynthetic electron transport chains (PETCs) of living photosynthetic organisms to redirect more electron flux toward an extracellular electrode. In this study, a semi‐artificial rewiring strategy, which use a water‐soluble fullerene derivative to capture electrons from PETCs and donate them for electrical current generation, is proposed. A positively charged fullerene derivative, functionalized with N,N‐dimethyl pyrrolidinium iodide, is found to be efficiently taken up by the cyanobacterium Synechocystis sp. PCC 6803. The distribution of this fullerene derivative near the thylakoid membrane, as well as site‐specific inhibitor assays and transient absorption spectroscopy, suggest that it can directly interact with the redox centers in the PETCs, particularly the acceptor side of photosystem I (PSI). The internalized fullerene derivatives facilitate the extraction of photosynthetic electrons and significantly enhance the photocurrent density of Synechocystis by approximately tenfold. This work opens up new possibility for the application of fullerenes as an excellent 3D electron carrier in living biophotovoltaics. [ABSTRACT FROM AUTHOR]

A new concept for the regioselective synthesis of Hamilton‐receptor and cyanurate‐functionalized oligo adducts of the fullerene C60 was developed. Based on an in‐situ deprotection and click‐post‐functionalization approach with novel azido precursors, the corresponding fullerene hexakis‐adducts with octahedral addition patterns and up to twelve Hamilton‐receptor/cyanurate moieties surrounding the fullerene sphere were synthesized. The versatility of this approach was further demonstrated by the synthesis of Hamilton‐receptor/cyanurate functionalized fullerene mono‐adducts, which are not accessible by direct cyclopropanation. Several fullerene target compounds were purified by simple washing procedures of the solid crude reaction mixture without the need for chromatography. The resulting fullerene mono‐ and hexakis‐adducts were fully characterized and their supramolecular properties were investigated by NMR‐spectroscopy and isothermal titration calorimetry (ITC). [ABSTRACT FROM AUTHOR]

By a reaction of trimethylphosphine with an open‐[60]fullerene, corresponding dimers could be generated via two‐fold deoxygenation processes even though the formation of β‐oxo‐phosphorous ylide is inevitable, a part of which is hydrolyzed to yield an α‐methylene carbonyl derivative. Nevertheless, Wittig reaction and aldol condensation did not proceed well, indicating the presence of an unknown dimerization pathway. In the ylide formation, 1‐phosphonium‐3‐carbabetaine was previously proposed as a key intermediate. Upon assuming that the betaine also participates in the dimerization process, we examined a possible reaction pathway computationally. As the results, the betaine formed by a reaction with the first phosphine was suggested to undergo nucleophilic addition to an unreacted molecule of the open‐[60]fullerene, yielding an epoxide dimer which is then deoxygenated by the second phosphine to furnish the desired open‐[60]fullerene dimer. [ABSTRACT FROM AUTHOR]

The document is the contents list for the journal "Chemical Communications" published on May 7, 2024. It includes a feature article on the chemistry of gold( I)– ethylene complexes, as well as several communications on various topics such as catalysis, organic synthesis, and electrochemistry. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document provides a list of articles and authors, along with images and permissions for reproduction. [Extracted from the article]

The Superatom Molecular Orbitals (SAMO) in fullerene derivatives are of great interests which gives a wide basement for many electronic applications. In this work, the Density Functional Theory reveals the SAMO states of endohedrally doped C80 derivatives with Li, Sc, Mn, Ti, Ca, Fe, and Co atoms in molecular and periodic structures. The choice and position of metal atoms in endohedrally doped C80 derivatives largely affects the orientation of SAMO energies and wavefunction distributions. Among various derivatives, the Co‐substituted C80 constitutes the lowest SAMO energy. The charge transfer study infers the influence of metal atoms inside the cage on SAMO energies. At higher energies, pz‐, 2s‐, and pxy‐ SAMO bands have been overlapped with higher dispersion bands which depict the increased intermolecular interaction in delocalized bands causing a larger dispersion. These results give new insights for future studies on lowering SAMO energy nearly to the fermi level in higher fullerenes. [ABSTRACT FROM AUTHOR]

To utilize the radical scavenging property of fullerene (C60), hydrophilic poly(ethylene glycol) (PEG) was chemically attached by Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The resulting C60-PEG derivatives were soluble in methanol when the molecular weight of PEG was 5,000. The antioxidative activity was evaluated for the alcohol-soluble C60 derivative. The C60-PEG has sufficient antioxidative activity with the β-carotene-attributed chromaticity of 76% for the C60-PEG derivative (9.96 mM). Further chemical modification will produce water-soluble fullerenes with higher antioxidative activities. [ABSTRACT FROM AUTHOR]

Drawing inspiration from the architecture of bacterial tentacles, a novel humidity-sensitive material has been engineered by grafting sulfonates onto the exterior of a fullerene cage. This innovative material with high hydrophilicity and fast response demonstrates superior humidity sensing capabilities, making it apt for non-contact humidity monitoring. [Display omitted] In this work, a straightforward method for synthesizing fullerene derivatives with tentacle structures has been explored for monitoring environmental humidity, which involves introducing sulfonate onto the fullerenes. The structure and number of polar groups in three fullerene derivatives determined by a series of structural tests greatly affect their hydrophilicity and morphology, resulting in changes in humidity sensitive properties. In particular, the hysteresis and response time of the sensors display a great correlation with hydrophilicity. C 60 -Ho, the best performing derivative of this work, has exhibited high response values (∼3500 times), good linearity (R2 = 97.3 %), and rapid response/recovery times (0.3/4.4 s), making it suitable for various applications such as non-contact detection of respiration, finger distance, and soil humidity. [ABSTRACT FROM AUTHOR]

The Superatom Molecular Orbitals (SAMO) in fullerene derivatives are of great interests which gives a wide basement for many electronic applications. In this work, the Density Functional Theory reveals the SAMO states of endohedrally doped C80 derivatives with Li, Sc, Mn, Ti, Ca, Fe, and Co atoms in molecular and periodic structures. The choice and position of metal atoms in endohedrally doped C80 derivatives largely affects the orientation of SAMO energies and wavefunction distributions. Among various derivatives, the Co‐substituted C80 constitutes the lowest SAMO energy. The charge transfer study infers the influence of metal atoms inside the cage on SAMO energies. At higher energies, pz‐, 2s‐, and pxy‐ SAMO bands have been overlapped with higher dispersion bands which depict the increased intermolecular interaction in delocalized bands causing a larger dispersion. These results give new insights for future studies on lowering SAMO energy nearly to the fermi level in higher fullerenes. [ABSTRACT FROM AUTHOR]

The reactions of cage‐opened C60 derivatives with aromatic diamines are known to cause an orifice‐enlargement in association with incorporating extended π‐systems. The present work focuses on 1,2‐, 2,3‐, and 1,8‐diaminonaphthalenes for the synthesis of a series of naphthalene‐fused fullerene derivatives. For the former two, orifice enlargement proceeded by cleaving two C=C bonds to afford an opening with a ring‐atom count of 20, in which the naphthalene moiety was fused by a pyrazine ring. For the reaction with 1,8‐diaminonaphthalene, only one C=C bond was cleaved to give a 17‐membered‐ring opening where the diaminonaphthalene moiety was fused by a pyrimidine ring. [ABSTRACT FROM AUTHOR]

The arene‐arene interactions between electron‐rich and deficient aromatics have been less understood. Herein, we focus on a [60]fullerene π‐surface as an electron‐deficient aromatics. Using a 1H signal of H2O@C60 as a magnetic probe, the presence of benzene–fullerene interactions was confirmed. To investigate substituent effects on the noncovalent arene‐fullerene interactions, NMR titration experiments were carried out using an open‐[60]fullerene and a series of substituted benzenes, i. e. PhX (X=NO2, CN, Cl, OMe, H, CH3, and NH2), demonstrating a 1 : 2 stoichiometry with a positive correlation between stabilization energies upon the first association (ΔG1) and Hammet constants (σm). The destabilization of the self‐assembled structure for X=OMe with a σ‐withdrawing nature clearly showed direct through‐space substituent‐π interactions describable by the Wheeler‐Houk model while the second association was suggested to be considerably perturbed by the secondary effects. [ABSTRACT FROM AUTHOR]

The relevance of the new forms of ecologically safe, stable in composition, in functional activity, biodegradable preparations development with a complex positive effect on plants remains high and the presented work is devoted to acquaintance with the generalized results of interdisciplinary studies for the effect on the system of soil (soil substitute)—cultivated plants by nanocompositions created based on carbon (water-soluble polyhydroxylated, carboxylated and amino acid derivatives of fullerene C60) nanostructures with additions of trace elements in certain concentration ratios. Based on the previously identified concentration ranges of the tested fullerene derivatives with a positive effect on plants when treating their seeds, introducing them into the soil, other root habitats and foliar exposure, their compositions with salts of trace elements were developed and in a series of vegetation and field experiments under controlled favorable conditions and when modeling oxidative stress caused by UV-B irradiation, deficiency of soil moisture, deficiency of nutrients, phytopathogens, as well as in the natural conditions of the Leningrad region, the main mechanisms of positive impact (regulatory on vital systems, adaptogenic, immunomodulatory, protective) of the created nanocompositions on plants and the prospects of their application in plant growing are shown. [ABSTRACT FROM AUTHOR]

Optically active left (M)‐ and right (P)‐handed helical syndiotactic poly(methyl methacrylate)s (M‐ and P‐st‐PMMAs) with a helicity memory enantioselectively encapsulated the racemic C60 derivatives, such as 3,4‐fulleroproline tert‐butyl ester (rac‐1) and tetraallylated C60 (rac‐2), as well as the C60‐bound racemic 310‐helical peptides (rac‐3) within their helical cavities to form peapod‐like inclusion complexes and a unique "helix‐in‐helix" superstructure, respectively. The enantiomeric excess (ee) and separation factor (enantioselectivity) (α) of the analyte 1 (ee = 23%–25% and α = 2.35–2.50) encapsulated within the helical cavities of the M‐ and P‐st‐PMMAs were higher than those of the analytes 2 and 3 (ee = 4.3%–6.0% and α = 1.28–1.50). The optically pure (S)‐ and (R)‐1 were found to more efficiently induce an excess one‐handed helical conformation in the st‐PMMA backbone than the optically pure (S)‐ and (R)‐1‐phenylethylamine, resulting in intense mirror‐image vibrational circular dichroism (VCD) spectra in the PMMA IR regions. The excess one‐handed helices induced in the st‐PMMAs complexed with (S)‐ and (R)‐1 were memorized after replacement with the achiral C60, and the complexes exhibited induced electric CDs in the achiral C60 chromophore regions. [ABSTRACT FROM AUTHOR]

The New Journal of Chemistry, published by The Royal Society of Chemistry, has released its latest issue which includes a variety of articles covering different topics in the field of chemistry. The papers discuss recent progress in areas such as nitrogen-heterocycles, chemisorption of gases, photoactive derivatives, and potential applications of nanoribbons. The journal aims to connect the global community with the chemical sciences and provides scientific insights and advancements in various fields of study. [Extracted from the article]

It was shown that the chain length of the aliphatic substituent in the alkyl derivative of 3-(1-indenyl)propionic acid of C60 and C70 fullerenes affects the efficiency of photovoltaic cells with the PTB7-Th:fullerene-derivative bulk heterojunction (BHJ). A series of new C60 and C70 fullerene derivatives containing the n-alkyl ester of 3-(1-indenyl)propionic acid were synthesized using the Diels–Alder reaction. The synthesized fullerene derivatives had aliphatic side chains of 4 to 12 carbon atoms in the ester group. All synthesized compounds were successfully used in the BHJ solar cell, achieving energy conversion efficiencies (PCEs) ranging from 0.8 to 3.9%. We observed an increase in solar cell open-circuit voltage of 30 meV for the 60IPH acceptor material. Long aging measurements of the solar cells with the new fullerene derivatives show long lifetimes for C60 derivatives and shorter for C70. The lifetime significantly depends on the aliphatic chain length. The longest 80% decay period, T80, was about 200 days. [ABSTRACT FROM AUTHOR]

Although fullerene derivatives such as [6,6]‐phenyl‐C61/C71‐butyric acid methyl ester (PC61BM/PC71BM) have dominated the the photoactive acceptor materials in bulk heterojunction organic solar cells (OSCs) for decades, they have several drawbacks such as weak absorption, limited structural tunability, prone to aggregation, and high costs of production. Constructing non‐fullerene small molecules with three‐dimensional (3D) molecular geometry is one of the strategies to replace fullerenes in OSCs. In this study, a 3D molecule, contorted hexa‐cata‐hexabenzocoronene tetra perylenediimide (HBC‐4‐PDI), was designed and synthesized. HBC‐4‐PDI shows a wide and strong light absorption in the whole UV‐vis region as well as suitable energy levels as an acceptor for OSCs. More importantly, the 3D construction effectively reduced the self‐aggregation of c‐HBC, leading to an appropriate scale phase separation of the blend film morphology in OSCs. A preliminary power conversion efficiency of 2.70 % with a champion open‐circuit voltage of 1.06 V was obtained in OSCs with HBC‐4‐PDI as the acceptor, which was the highest among the previously reported OSCs based on c‐HBC derivatives. The results indicated that HBC‐4‐PDI may serve as a good non‐fullerene acceptor for OSCs. [ABSTRACT FROM AUTHOR]

The bulk-heterojunction (BHJ) system that uses a π -conjugated polymer as an electron donor, and a fullerene derivative as an electron acceptor, is widely used in organic solar cells (OSCs) to facilitate efficient charge separation and extraction. However, the conventional BHJ system still suffers from unwanted phase segregation caused by the existence of significant differences in surface energy between the two BHJ components and the charge extraction layer during film formation. In the present work, we demonstrate a sophisticated control of fast film-growth kinetics that can be used to achieve a uniform distribution of donor and acceptor materials in the BHJ layer of OSCs without undesirable phase separation. Our approach involves depositing the BHJ solution onto a spinning substrate, thus inducing rapid evaporation of the solvent during BHJ film formation. The fast-growth process prevents the fullerene derivative from migrating toward the charge extraction layer, thereby enabling a homogeneous distribution of the fullerene derivative within the BHJ film. The OSCs based on the fast-growth BHJ thin film are found to exhibit substantial increases in JSC, fill factor, and a PCE up to 11.27 mA/cm2, 66%, and 4.68%, respectively; this last value represents a remarkable 17% increase in PCE compared to that of conventional OSCs. [ABSTRACT FROM AUTHOR]

In this paper, the thermal stability and degradation mechanisms of C60 fullerene‐based polymers, obtained by click polymerization between dialkyne‐substituted C60 derivative monomers and 1,3,5‐tris(dodecyloxy)benzene‐based diazide comonomers, were evaluated. The activation energy of the fullerene polymer C60P2 with an ethylene spacer, determined under peak degradation rate conditions, was lower than that of the counter polymer C60P1 with a methylene spacer, suggesting lower thermal stability of C60P2. The combined technique of thermogravimetric analysis—mass spectroscopy and Fourier transform infrared spectroscopy revealed that the thermal decomposition onset of the analyzed samples is accompanied by CC cleavage of the dodecyloxyside chain groups, followed by the decomposition of the 1,2,3‐triazole, dicarboxylate and benzoate moieties. It was found that no thermal decomposition of the fullerene carbon cage occurs up to 670°C. Molecular modeling with Hyperchem software version 7.5 confirmed that C60P1 is more thermally stable than C60P2. [ABSTRACT FROM AUTHOR]

Organic solar cells (OSCs) enjoy a huge market and public attention as an emerging renewable and clean energy source due to their accessibility, sustainability, translucency, good flexibility, non-toxicity, and low preparation cost. However, the choice of an acceptor material is now the pivotal factor restricting the development of OSCs. To continuously improve stability and increase power conversion efficiency (PCE) for better performance, highperformance acceptor materials are an important part of enabling OSCs. From fullerenes and their derivatives and non-fullerenes, we sum up the latest research progress on high-performance acceptor materials for OSCs and then introduce the synthesis methods of non-fullerenes. The latest strategies to enhance the performance of organic solar cells and the wide range of applications of non-fullerene acceptors (NFAs) on different OSCs are also discussed. In addition, challenges faced by OSCs in improving their performance and the prospects for future development are revealed, providing new ideas for designing the next generation of high-performance OSCs. [ABSTRACT FROM AUTHOR]

Results are given for a kinetic study of the synthesis of a new fullerene derivative containing a diterpene fragment obtained using HPLC and subsequent mathematical modelling. Kinetic and activation parameters were found for the cyclopropanation of fullerene using the Bingel procedure and a reaction mechanism was proposed. The optimal synthesis conditions were found to entail a slight excess of a chlorine‑containing cyclopropanation agent and carrying out the reaction at room temperature. [ABSTRACT FROM AUTHOR]

In order to maximally reduce the toxicity of fullerenol (the first derivative of C60, FD-C60), and increase its biomedical efficiency, the second derivative SD-C60 (3HFWC, Hyper-Harmonized Hydroxylated Fullerene Water Complex) was created. Several different methods were applied in the comparative characterization of FD-C60 and SD-C60 with the same OH groups in their core. FD-C60 as an individual structure was about 1.3 nm in size, while SD-C60 as an individual structure was 10–30 nm in size. Based on ten physicochemical methods and techniques, FD-C60 and SD-C60 were found to be two different substances in terms of size, structure, and physicochemical properties; FD-C60, at 100 °C, had endothermic characteristics, while SD-C60, at 133 °C, had exothermic characteristics; FD-C60 did not have water layers, while SD-C60 had water layers; the zeta potential of FD-C60 was −25.85 mV, while it was −43.29 mV for SD-C60. SD-C60 is a promising substance for use in cosmetics and pharmaceuticals. [ABSTRACT FROM AUTHOR]

An open-cage bis[60]fulleroid (OC) was applied as an electron transport material (ETM) in tin (Sn) halide perovskite solar cells (PSCs). Due to the reduced offset between the energy levels of Sn-based perovskites and ETMs, the power conversion efficiency (PCE) of Sn-based PSCs with OC reached 9.6% with an open-circuit voltage (VOC) of 0.72 V. Additionally, OC exhibited superior thermal stability and provided 75% of the material without decomposition after vacuum deposition. The PSC using vacuum-deposited OC as the ETM could afford a PCE of 7.6%, which is a big leap forward compared with previous results using vacuum-deposited fullerene derivatives as ETMs. [ABSTRACT FROM AUTHOR]

In this study we present a method for functionalizing C60 through a Rh‐catalyzed cyclization reaction with 1,6‐enynes, resulting in the formation of a fused bicyclic structure. Additionally, fullerene derivatives are further functionalized through regioselective photooxygenation reactions. Our DFT calculations reveal two distinct reaction pathways: one involving rhodium‐catalyzed cycloisomerization of the enyne followed by Diels‐Alder with C60, and the other featuring a rhodium‐catalyzed [2+2+2] cycloaddition of enyne and C60 followed by isomerization. Surprisingly, both pathways exhibit nearly identical energy barriers. However, experimental tests indicate that the predominant pathway varies depending on the substitution motifs of the substrates. [ABSTRACT FROM AUTHOR]

Fullerene-derivatives based bulk heterojunctions hold an exceptionally important role on the roadmap of highly efficient organic solar cells (OSCs). In recent years, the utilization of the non-fused ring acceptors based OSCs has further improved photovoltaic power conversion efficiencies. Among these, one of the fundamental issues is to explore and to understand the spin-related polaron dissociation at charge transfer states because they act as the central unit for the photovoltaic action. It is also eagerly important to quantify some internal fields, such as hyperfine fields and the spin–orbit coupling. The aim of the work is to develop a method for unraveling the photoexcited spin states, particularly for the fullerene-derivative based OSC. Furthermore, it helps to elucidate a long-standing issue regarding the relatively high production of photocurrent for the P3HT:PC71BM system, which is indeed contrary to its counterpart the P3HT:PC61BM system. Their corresponding Jablonski diagrams have been determined in order to understand interior spin dynamics. The method of the study offers an alternative route for an understanding of device performance from the spin-related aspect. [ABSTRACT FROM AUTHOR]

The polymerization of fullerenes is a significant method for obtaining fullerene-based materials that possess intriguing properties. Metallofullerenes, as a notable type of fullerene derivatives, are also capable of undergoing polymerization, potentially resulting in the creation of metallofullerene polymers. However, there is currently limited knowledge regarding the polymerization process of metallofullerenes. In this study, we have selected Ca@C   60 as a representative compound to investigate the polymerization process of metallofullerenes. The objective of this research is to determine whether the polymerization process is energetically favorable and to examine how the electronic properties of the metallofullerene are altered throughout the polymerization process. Ca@C   60 is a unique metallofullerene molecule that exhibits insolubility in common fullerene solvents like toluene and carbon disulfide but is soluble in aniline. This behavior suggests a potential tendency for Ca@C   60 to form oligomers and polymers that resist dissolution. However, the structures and properties of polymerized Ca@C   60 remain unknown. We employed density functional theory calculations to investigate the stability and electronic properties of one-dimensional and two-dimensional Ca@C   60 oligomers and polymers. Our findings indicate that the coalescence of Ca@C   60 monomers is energetically favorable, with a significant contribution from van der Waals interactions between the fullerene cages. The polymerization process of Ca@C   60 also involves the formation of covalent linkages, including four-atom rings and C-C single bonds. The increase in the number of the Ca@C   60 units to three and four in the oligomer leads to a significant decrease in the HOMO-LUMO gap. In the two-dimensional polymerized Ca@C   60 , the organization of the monomers closely resembles the spatial configuration of carbon atoms in graphene. With a direct bandgap of 0.22 eV, the polymerized Ca@C   60 holds potential for utilization in optoelectronic devices. [ABSTRACT FROM AUTHOR]

Spin frustration, which results from geometric frustration and a systematical inability to satisfy all antiferromagnetic (AF) interactions between unpaired spins simultaneously, is under the spotlight for its importance in physics and materials science. Spin frustration is treated as the structural basis of quantum spin liquids (QSLs). Featuring flexible chemical structures, organic radical species exhibit great potential in building spin‐frustrated molecules and lattices. So far, the reported examples of spin‐frustrated organic radical compounds include triradicals, tetrathiafulvalene (TTF) radicals and derivatives, [Pd(dmit)2] compounds (dmit=1,3‐dithiol‐2‐thione‐4,5‐dithiolate), nitronyl nitroxides, fullerenes, polycyclic aromatic hydrocarbons (PAHs), and other heterocyclic compounds where the spin frustration is generated intra‐ or intermolecularly. In this Minireview, we provide a brief summary of the reported radical compounds that possess spin frustration. The related data, including magnetic exchange coupling parameters, spin models, frustration parameters, and crystal lattices, are summarized and discussed. [ABSTRACT FROM AUTHOR]

Fullerene derivatives have been used as electron acceptor and transport materials in organic photovoltaics as well as in perovskite solar cells. Among them, [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC61BM) has been one of the most widely used, in combination with poly‐3‐hexylthiophene (P3HT) as an electron donor semiconducting polymer, for the fabrication of organic bulk heterojunction solar cells (BHJ‐OSC). In this work, a steroid‐fullerene hybrid was synthesized through the Bingel–Hirsch reaction to compare its properties with PC61BM as the reference structure. Different spectroscopic techniques were employed to characterize the new fullerene derivative, namely 1D and 2D nuclear magnetic resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), and high‐resolution mass spectrometry (HRMS). In addition, thermogravimetric analysis (TGA), and cyclic voltammetry were also performed. The characterization was completed by transmission electron microscopy (TEM), which explore the hybrid's morphology, where the presence of the steroid moiety increases the solubility of the fullerene material. DFT/PBE−D3(BJ)/6‐311G(d,p) calculations for both the steroid‐fullerene hybrid and PC61BM allowed to obtain geometry optimizations and electronic structure data. A comparative study to analyze the nature of the electronic properties of the synthesized steroid‐[60]fullerene hybrid and PC61BM with an oligomer of ten thiophene units, used in the active layer of organic solar cells, was carried out. Electron density maps using the [CIS|CNDOL/21] approach illustrate the photoexcitation of the donor followed by an electron‐charge transfer to the acceptor fullerene. [ABSTRACT FROM AUTHOR]

New possibilities of the photochemical addition to fullerene С60 were demonstrated. Monosubstituted 1,9-dihydrofullerenes were obtained by irradiation of С60 in the presence of homologues of thiophene, pyridine, and naphthalene as well as esters of glutaric, phthalic, succinic, adipic, pyridinedicarboxylic acids and N-alkyllactam. The HC60 moiety is bound to the hydrocarbon part of the organic fragment. The product of the methyl glutarate addition was reduced by bis(arene)chromium to give a new ion-radical salt. [ABSTRACT FROM AUTHOR]

New possibilities of the photochemical addition to fullerene С60 were demonstrated. Monosubstituted 1,9-dihydrofullerenes were obtained by irradiation of С60 in the presence of homologues of thiophene, pyridine, and naphthalene as well as esters of glutaric, phthalic, succinic, adipic, pyridinedicarboxylic acids and N-alkyllactam. The HC60 moiety is bound to the hydrocarbon part of the organic fragment. The product of the methyl glutarate addition was reduced by bis(arene)chromium to give a new ion-radical salt. [ABSTRACT FROM AUTHOR]

As a typical representative of water-soluble fullerene derivatives, fullerenols have been widely used in biomedicine, adsorption, and sensor detection. This paper has studied the structure and composition of commercial fullerenols, which indicate abundant hydrophilic groups exist on the surface of carbon cages to promote the adsorption of water molecules. It is found that the humidity sensor coated with fullerenols has a fast response (19s)/recovery time (12s) and low hysteresis (ΔH ≈ 2.68%RH) at the relative humidity level of 11–97%. The change mechanism of the impedance signal is due to the ions' formation caused by the adsorption of water molecules. Excellent repeatability and stability are still maintained after a long time of exposure in the air, which displays great application potential. [ABSTRACT FROM AUTHOR]

In this study, seven new molecules (OA1–OA7) were introduced with the goal of enhancing the photovoltaic efficiency of solar cells. All these molecules were evaluated by using density functional theory (DFT). All the designed molecules have shorter band gap and higher values of λ m a x than the reference. For confirming the charge mobility, the optoelectronic characterization has been carried out by densities of states (DOS), transition density matrix (TDM), molecular electrostatic potential (MEP) and reorganization energy. The V o c values in designed molecules were also improved. The stability of designed molecules was also confirmed by the analysis of non-covalent interactions (NCIs). These results elaborate on the superiority of these novel-designed molecules over pre-existing (R) molecule as potential blocks for better organic solar cell applications. In this work, a series of seven new molecules (OA1 to OA7) is presented to potentially improve the photovoltaic efficiency of organic solar cells. Newly presented molecules exhibited improved absorption spectra and narrow band gap. Proposed molecules show improved optoelectronic properties which make them a superior choice than the reference molecule. [ABSTRACT FROM AUTHOR]

The human body contains 60–70% water, depending on age. As a body fluid, it is not only a medium in which physical and chemical processes take place, but it is also one of the active mediators. Water is the richest substance with non-covalent hydrogen bonds. Water molecules, by themselves (in vacuum), are diamagnetic but when organized into clusters, they become diamagnetic or paramagnetic. Also, biomolecules (DNA, collagen, clathrin, and other proteins) have non-covalent hydrogen bonds in their structure. The interaction, as well as signal transmission, between water and biomolecules is achieved through the vibrations of covalent and non-covalent hydrogen bonds, which determine the state and dynamics of conformational changes in biomolecules. Disruptive conformational changes in biomolecules, cells, and tissues lead to their dysfunctionality, so they are a frequent cause of many disorders and diseases. For example, the rearrangement of hydrogen bonding due to mitochondrial disease mutation in cytochrome bc1 disturbs heme bH redox potential and spin state. In order to prevent and repair the dysfunctional conformational changes, a liquid substance was developed based on the second derivative of the C60 molecule (SD-C60), which has classical and quantum properties. The characterization of SD-C60 by UV-VIS-NIR, FTIR, TEM, and AFM/MFM was performed and it is shown that SD-C60 water layers generate vibrations with near-zero phase dispersion which are transmitted through Fibonacci's water chains to biomolecules. In comparison with previously published SD-C60 derivate (3HFWC, size until 10 nm, and 1–5 water layers), the improved formulation (3HFWC-W, size 10–25 nm, and 6–9 water layers) showed multiplied cytotoxic activity against melanoma cell lines of different aggressiveness. Apart from this, the mode of action was preserved and based on an induction of senescence rather than cell death. Importantly, high selectivity towards malignant phenotypes was detected. Observed effects can be ascribed to a machinery of hydrogen bonds, which are generated in SD-C60 and transmitted through water to biomolecules. This approach may open a new field in science and healthcare—a "water-based nanomedicine". [ABSTRACT FROM AUTHOR]

Compared with perovskite solar cells and silicon solar cells, the excessive voltage loss (Vloss) becomes a stubborn stone that seriously hinders the further improvement of organic photovoltaic (OPV). Thus, many researchers focus on finding an effective material system to achieve high-performance OPVs with low Vloss. In recent 5 years, acceptor-donor-acceptor'-donor-acceptor (A-DA'D-A) type non-fullerene acceptors (NFAs) have attracted great attention because of their promising photovoltaic performance. Among them, A-DA'D-A type NFAs containing non-halogenated end group (NHEG) exhibit the large potential to achieve high open-circuit voltage (VOC) for the state-of-the-art OPVs, because of high-lying molecular energy levels and decreasing Vloss. In this review, we systematically summarize the recent development of A-DA'D-A type NHEG-NFAs and the impact of different NHEGs on the optoelectronic properties as well as the photovoltaic performance. In addition, we especially analyze the Vloss of NHEG-NFAs in the binary and ternary OPV devices. At last, we provide perspectives on the further molecular design and future challenges for this kind of materials as well as suggested solutions. [ABSTRACT FROM AUTHOR]

[Display omitted] Methoxy groups on the fullerene cage in compound C 60 (OMe) 5 Br were displaced by thiol residues of methyl 3-mercaptopropanoate thus leading to C 60 (SCH 2 CH 2 CO 2 Me) 5 H product. The structure of the product was established by NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Cyclopent-4-ene-1,3-diones fused with heterocycles are important electron-withdrawing anchor groups in the design of non-fullerene acceptors that find applications in organic bulk heterojunction solar cells. This microreview summarizes synthesis of these heterocyclic compounds to create non-fullerene acceptors and their use in highly efficient solar cells. [ABSTRACT FROM AUTHOR]

[Display omitted] The supramolecular complexation of anthracycline antibiotic ruboxyl with water-soluble fullerene derivative was visualized by scattering scanning near-field optical microscopy, and the effects of this complexation on the antileukemic activity in vivo were evaluated. Treatment of mice with P388 lymphocytic leukemia with ruboxyl resulted in 13% of cured animals, while similar treatment with ruboxyl–fullerene derivative combination caused 63% curing. [ABSTRACT FROM AUTHOR]

Due to its high electron affinity and electron mobility in a wide absorption range of the visible solar spectrum, [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) is often used as an efficient acceptor in organic photovoltaics. In turn, imines are additives to the active layer of organic solar cells, mainly due to the free electron pair of the imine nitrogen atom and the presence of various chemical groups affecting the polarity and conformations of molecules. However, the attainable efficiency is not as high as expected. Therefore, we have systematically investigated two imines and their mixtures with PC71BM by spectroscopic (the high pressure UV–Vis and frequency domain dielectric), thermoelectric, and mechanical methods for organic, flexible photovoltaics. Both the imines, (N,NʹE,N,NʹE)-N,Nʹ-([2,2ʹ:5ʹ,2ʺ-terthiophene]-5,5ʺ-diylbis(methanylylidene))bis(benzo[d]thiazol-2-imine) (SC3) and (6E)-N-((5-(5-(5-((E)-(4-(4-(4-fluorophenyl)thiazol-2-yl)phenylimino)methyl)thiophen-2-yl)thiophen-2-yl)thiophen-2-yl)methylene)-4-(4-(4-fluorophenyl)thiazol-2-yl)benzenamine (SC13), have the same core composed of three thiophene rings but different terminal chains of the molecules. In the imine SC3, the imine bond is followed by benzothiazole rings on both sides of the core, while in SC13, a thiazole ring separates two benzene rings, the terminal one F-substituted. The difference in molecular structure affects the electric properties of the neat imine and its mixed layers. An addition of PC71BM to the imines improves their electric conductivity. The mechanical studies focused on the stress at break and elongation showed superior behaviour compared to fullerene derivative. High pressure systematically reduces the band gap energy, Eg, from 1.68 eV at 0.16 GPa to 1.51 eV at 2.69 GPa for PC71BM, from 1.77 eV at 0.1 MPa to 1.53 eV at 4.15 GPa for SC3, and from 1.99 eV at 0.11 GPa to 1.8 eV at 3.10 GPa for SC13, as determined by the UV–Vis absorbance measurements in a diamond-anvil cell. These Eg reductions reflect the compressed intermolecular interactions that can be used to monitor the structural stability of these compounds. Based on the dielectric studies it was found that the relaxation processes registered for both imines are probably the grain boundary relaxation. Two processes also appear in the systems with PC71BM, but none of them is the one characteristic of imines. The high-frequency process has a dipole character while the low-frequency one is probably the grain boundary relaxation of these systems. The mechanism of quasi-DC conduction in various temperature ranges in the studied systems was also determined. [ABSTRACT FROM AUTHOR]

[Display omitted] Titanium dioxide (TiO 2) is regularly used as an electron transport material in n -i-p perovskite solar cells (PSCs). However, massive defects exist on the TiO 2 surface, which will lead to serious hysteresis and interface charge recombination of the device, thus affecting the device's efficiency. In this study, a cyano fullerene pyrrolidine derivative (C 60 -CN) was synthesized and applied to PSCs for the first time to modify the TiO 2 electron transport layer. Systematic studies have shown that the addition of the C 60 -CN modification layer on the TiO 2 surface will enlargement the perovskite grain size, improve the perovskite film quality, enhance electron transport, and reduce charge recombination. The C 60 -CN layer can significantly reduce the density of trap states in the perovskite solar cells. As a result, the PSCs based on C 60 -CN/TiO 2 obtained a power conversion efficiency (PCE) of 18.60%, suppressing the hysteresis and improving the stability, whereas the PCE of the control device using the original TiO 2 ETL was lower, 17.19%. [ABSTRACT FROM AUTHOR]

Perovskite films prepared by the solution process usually result in irregular grain orientation and rich buried interface defects, hindering the further improvement of device performance. Herein, multi‐fluorine‐containing C60‐ and C70 (higher fullerene)‐porphyrin derivatives, F60PD and F70PD, are synthesized and pre‐buried to modify the SnO2/perovskite heterointerface. The F70PD modification layer provides a better perovskite quality and more effective electron transporting capability compared to the corresponding F60PD, with the F70PD being more effective in regulating the perovskite growth, passivating the buried interface defects, and optimizing the interface energy level alignment. Consequently, the F70PD‐based device delivers superior efficiency and stability than the control and F60PD‐based devices. The F70PD‐based device yields a champion efficiency of 24.09% with negligible hysteresis. Meanwhile, due to the increased activation energy of ion migration, the F70PD‐based device maintains 80% of its initial efficiency after operating at the maximum power point for 1620 h. This study highlights the potential of designing higher fullerene materials for buried interface to further improve the perovskite solar cells' performance. [ABSTRACT FROM AUTHOR]

The results of this experiment showed the effect of hybrid nanostructures (HNS) based on amino acid derivatives of fullerene C60 and derivatives of vitamin B12 (T1, T2) on the growth of wheat (Triticum aestivum L.) seeds in laboratory. Seeds treated with distilled water were used as the control (T0). Seeds treated by complexes T1–T3 pump spraying at the concentration of 10−5 M increased germination to 10–14%, while shoots height increased to 21–34% compared to the control. Treatment with these complexes enabled plants to survive water stress. The relative water content RWC in these samples was 11–21% higher than in the control. The results obtained demonstrate the possibility of using these hybrid compounds to achieve better seedlings and increase the drought resistance of wheat. [ABSTRACT FROM AUTHOR]

In this study, we prepared amine‐functionalized fullerene derivatives by using methylene blue (MB)‐sensitized photoaddition reactions of fullerene C60 with a variety of α‐silyl group containing N‐alkylglycinates through 1,3‐dipolar cycloaddition reactions of in situ formed azomethine ylide, derived from glycinates, to fullerene C60 and examined their solubility properties in several organic solvents. The results showed that although it was hard to find a clear correlation between the solvent solubility of and N‐substituents of fullereopyrrolidines, the solubility of functionalized fullerene derivatives in organic solvents such as toluene, CHCl3, CH2Cl2, and tetrahydrofuran (THF) was much higher than that of C60 and in addition, the solubility properties of fullereopyrrolidines can be manipulated by incorporating diverse organic moieties into fullerene surface. [ABSTRACT FROM AUTHOR]