Easy, efficient and versatile one-pot synthesis of Janus-type-substituted fullerenols

• Marius Kunkel and
• Sebastian Polarz

Beilstein J. Org. Chem. 2019, 15, 901–905, doi:10.3762/bjoc.15.87

• steps involved. Fullerene derivatives are of great interest in numerous research areas such as biological sciences and materials sciences [4][5][6][7][8][9]. A vast amount of synthetic protocols have been developed over the years to modify fullerenes [10][11][12][13]. A particular task was to provide

• fullerenes with solubility in water. Thus, one important class of fullerene derivatives are the hydroxylated and polyhydroxylated compounds, so called fullerenols (C60(OH)n) [14]. The degree of hydroxylation and with that the solubility of these compounds can be tuned by using different synthetic approaches

Fabrication of supramolecular cyclodextrin–fullerene nonwovens by electrospinning

• Hiroaki Yoshida,
• Ken Kikuta and
• Toshiyuki Kida

Beilstein J. Org. Chem. 2019, 15, 89–95, doi:10.3762/bjoc.15.10

• supramolecular fiber materials composed of cyclodextrin (CD)–fullerene inclusion complexes by electrospinning. Similar to the molecular state of fullerenes in solution, the resulting fibers include molecularly-dispersed fullerenes. We believe such a concept could be expanded to diverse host–guest complexes

• promising as an approach for fiber functionalization, the scope is limited to cases with 1:1 inclusion complexes and chemically modified CD. Fullerenes have been widely studied in the fields of chemistry and materials science because they have attractive chemical structures and good electron acceptor

• abilities for free radical scavengers and solar cell applications [18][19][20]. A serious issue for practical applications of fullerenes is the poor solubility in most solvents. Various methods to improve the solubility have been demonstrated by coating the surface with surfactants or host molecules and

Calixazulenes: azulene-based calixarene analogues – an overview and recent supramolecular complexation studies

• Paris E. Georghiou,
• Shofiur Rahman,
• Abdullah Alodhayb,
• Hidetaka Nishimura,
• Jaehyun Lee,
• Atsushi Wakamiya and
• Lawrence T. Scott

Beilstein J. Org. Chem. 2018, 14, 2488–2494, doi:10.3762/bjoc.14.225

•  1) and on its mechanochemically-generated solid-state complex of C60-fullerene [17]. This all-hydrocarbon, wide-rim octaphenyl-functionalized calix[4]azulene was designed to evaluate its potential for encapsulating C60 or C70 fullerenes. The lack of sufficient solubility of 5 in common organic

• solvents prevented a fuller examination of its potential supramolecular properties with fullerenes, a topic of particular interest to us [18]. Therefore, the solid state supramolecular complexation properties of 5 were experimentally studied using solid state NMR and XRD experiments, and also theoretically

A conformationally adaptive macrocycle: conformational complexity and host–guest chemistry of zorb[4]arene

• Liu-Pan Yang,
• Song-Bo Lu,
• Arto Valkonen,
• Fangfang Pan,
• Kari Rissanen and
• Wei Jiang

Beilstein J. Org. Chem. 2018, 14, 1570–1577, doi:10.3762/bjoc.14.134

• in plots of ΔH versus temperature from 283 to 313 K (Figure 5). The release of solvent molecules upon complex formation may account for the negative heat capacity change and similar heat capacity changes were also reported for the fullerenes recognition [40]. Meanwhile, the changes of ΔG for the

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

Mechanochemistry-assisted synthesis of hierarchical porous carbons applied as supercapacitors

• Desirée Leistenschneider,
• Nicolas Jäckel,
• Felix Hippauf,
• Volker Presser and
• Lars Borchardt

Beilstein J. Org. Chem. 2017, 13, 1332–1341, doi:10.3762/bjoc.13.130

• ]. For example, the preparation of nanocarbon structures such as graphene sheets or fullerenes [39][40][41] as well as porous carbonaceous polymers [42][43] have been conducted mechanochemically. Our work demonstrates that a templating approach can be transferred into the solvent-free environment of a

Supramolecular frameworks based on [60]fullerene hexakisadducts

• Andreas Kraft,
• Johannes Stangl,
• Ana-Maria Krause,
• Klaus Müller-Buschbaum and
• Florian Beuerle

Beilstein J. Org. Chem. 2017, 13, 1–9, doi:10.3762/bjoc.13.1

• . Keywords: fullerenes; hexakisadducts; hydrogen bonding; porous materials; structure elucidation; Introduction The utilization of confined nanospace in rigid frameworks [1], which are derived from small molecular precursors under dynamic conditions, has emerged as a novel design paradigm for functional

• (left part of Figure 4). Interestingly, this packing motif results in the interpenetration of two independent hydrogen bonding networks (indicated in purple and cyan in Figure 5). Therefore, the individual layers are densely packed exhibiting linear columns of fullerenes in van-der-Waals distance

Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

• Forrest S. Etheridge,
• Roshan J. Fernando,
• Sandra Pejić,
• Matthias Zeller and
• Geneviève Sauvé

Beilstein J. Org. Chem. 2016, 12, 1925–1938, doi:10.3762/bjoc.12.182

• and non-planar molecule with low electron transfer reorganization energy, further supporting its potential to replace fullerenes in OPVs [12]. However, the HOMO and LUMO energy levels of Zn(WS3)2 in solution are higher than that of the most popular electron acceptor phenyl-C61-butyric acid methyl

Organic chemistry meets polymers, nanoscience, therapeutics and diagnostics

• Vincent M. Rotello

Beilstein J. Org. Chem. 2016, 12, 1638–1646, doi:10.3762/bjoc.12.161

• supramolecular chemistry, along with a project in fullerenes [6][7]. After finishing my postdoctoral work, I moved to the University of Massachusetts. I chose UMass based on its quality and longstanding reputation for collaborative research. Upon arrival, I collected a fired up group of graduate students and

• went to it. I maintained my fullerenes project [8], and initiated a set of three other supramolecular projects. Of these projects, our work on flavoenzyme models was the one that really took off. Using electrochemistry, we were able to gain a real understanding of how forces such as hydrogen bonding [9

Separation and identification of indene–C₇₀ bisadduct isomers

• Bolong Zhang,
• Jegadesan Subbiah,
• David J. Jones and
• Wallace W. H. Wong

Beilstein J. Org. Chem. 2016, 12, 903–911, doi:10.3762/bjoc.12.88

• . Fullerenes and their derivatives are widely used in BHJ OSC devices as the electron acceptor material. They have several characteristics that make them favorable for this application including good electron transport [2], reversible reduction behavior [3], and easily functionalized structures [4]. Indene

• ]. As a consequence, it was envisaged that the fullerene derivatives with smaller π-conjugated area would interact less strongly with the stationary phase of the column and therefore elute faster than derivatives with larger π-surface. In addition, the substitution on fullerenes may block the

Life lessons

• Jonathan R. Nitschke

Beilstein J. Org. Chem. 2015, 11, 2350–2354, doi:10.3762/bjoc.11.256

• materials. Three of these containers are shown below: Figure 2a depicts an FeII8L6 cubic cage with walls constructed from porphyrins that binds guests such as fullerenes and coronene [26]; Figure 2b shows a CoII10L15 pentagonal prism that embeds five anions, such as PF6− (shown) or ClO4− in its walls, and a

Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

• Masahiko Iyoda and
• Masashi Hasegawa

Beilstein J. Org. Chem. 2015, 11, 1596–1613, doi:10.3762/bjoc.11.175

• examples [30][31][32][33]. Other functional units such as fullerenes [34][35], cyclodextrins [36], porphyrin [37], and phthalocyanine [38][39][40] can also be introduced into the core of radial oligo-TTFs. As shown in Figure 1, TTF-annelated porphyrin 1 was synthesized by Becher and co-workers in 2001 [37

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• area due to the cost and energy demanding purification process and the poor processibility of the fullerenes. To this end, Zhang and co-workers [140] reported the synthesis of the bisporphyrin macrocycle 144 with an adaptable cavity by using alkyne metathesis with high efficiency. Tamm and co-workers

Donor–acceptor type co-crystals of arylthio-substituted tetrathiafulvalenes and fullerenes

• Xiaofeng Lu,
• Jibin Sun,
• Shangxi Zhang,
• Longfei Ma,
• Lei Liu,
• Hui Qi,
• Yongliang Shao and
• Xiangfeng Shao

Beilstein J. Org. Chem. 2015, 11, 1043–1051, doi:10.3762/bjoc.11.117

• , those involving fullerene molecules are of growing interest due to their potential application in organic voltaics [20]. The TTF–fullerene dyad is a typical donor–acceptor (D–A) system, where TTFs and fullerenes act as donors and acceptors, respectively. The TTF–fullerene dyad can be constructed by (1

• between TTFs and fullerenes are key factors that give rise to the effective surface contact for the stabilization of the resulting supramolecular structures. Because pristine TTF cannot form good enough surface contact with fullerenes due to the shape and size mismatch [42], chemical modifications of TTF

• have been carried out. To this regard, introduction of substituents onto the peripheral sites [43][44][45][46][47][48][49][50][51][52][53][54] and expansion of the π-systems have been reported [55][56][57][58][59]. As reported, the π-extended TTFs (exTTF) can encapsulate fullerenes in solution, and

Copper ion salts of arylthiotetrathiafulvalenes: synthesis, structure diversity and magnetic properties

• Longfei Ma,
• Jibin Sun,
• Xiaofeng Lu,
• Shangxi Zhang,
• Hui Qi,
• Lei Liu,
• Yongliang Shao and
• Xiangfeng Shao

Beilstein J. Org. Chem. 2015, 11, 850–859, doi:10.3762/bjoc.11.95

• ]. Consequently, the complexes of Ar-S-TTFs with electron acceptors such as fullerenes [40][41] and TCNQ [42] show a neutral ground state. However, Ar-S-TTFs can be chemically oxidized by strong electron acceptors such as F4TCNQ [42] and Keggin-type phosphomolybdic acid [43] to form CT complexes. In comparison

• with fullerenes and TCNQ, the inorganic salt CuX2 (X = Cl, Br) is a strong oxidant and has been used to oxidize the TTFs to form organic conductors with diverse electronic ground states [44][45][46][47][48][49][50][51][52][53][54]. Herein, we report the synthesis, structure, and magnetic properties of

Mechanical stability of bivalent transition metal complexes analyzed by single-molecule force spectroscopy

• Manuel Gensler,
• Christian Eidamshaus,
• Maurice Taszarek,
• Hans-Ulrich Reissig and
• Jürgen P. Rabe

Beilstein J. Org. Chem. 2015, 11, 817–827, doi:10.3762/bjoc.11.91

• forces from 280 pN to 610 pN at ln(dF/dt) = 8.5 [10]. On the single-molecular level, the interaction between Zn-porphyrine and C60 fullerenes shows a similar trend comparing their monovalent and bivalent interaction [37]. The latter has a shorter rupture length, lower thermal off-rate and consequently

Mono- and multilayers of molecular spoked carbazole wheels on graphite

• Stefan-S. Jester,
• A. Vikas Aggarwal,
• Daniel Kalle and
• Sigurd Höger

Beilstein J. Org. Chem. 2014, 10, 2783–2788, doi:10.3762/bjoc.10.295

• resistivity. Coadsorption on a (supra-)molecular template is rather an exception than a rule. However, when observed, it is often between electron-rich macrocycles that act as hosts for electron-deficient guest molecules (e.g., fullerenes, metallacycles) [14][15]. In the case here, the adlayer stability can

Synthesis of nanodiamond derivatives carrying amino functions and quantification by a modified Kaiser test

• Gerald Jarre,
• Steffen Heyer,
• Elisabeth Memmel,
• Thomas Meinhardt and
• Anke Krueger

Beilstein J. Org. Chem. 2014, 10, 2729–2737, doi:10.3762/bjoc.10.288

• depicted in Scheme 1. Besides the novel functionalization methods using pyrazines and cyclobutenes (see below) several nanodiamond conjugates were prepared for comparison similar to already reported procedures. It is known that pyrazine derivatives react with fullerenes in a cycloaddition reaction [13

• . This system has been successfully used for the functionalization of fullerenes [15]. The precursor 8 was synthesized according to Martinez et al. starting from cyclobutanone and methyl thiocyanate [16]. The cyclobutene ring opens at temperatures around 190 °C and the ortho-quinodimethane is formed in

Chiral phosphines in nucleophilic organocatalysis

• Yumei Xiao,
• Zhanhu Sun,
• Hongchao Guo and
• Ohyun Kwon

Beilstein J. Org. Chem. 2014, 10, 2089–2121, doi:10.3762/bjoc.10.218

• 79–94% ee (Scheme 7) [40]. Very interestingly, when using the chiral phosphine (S,S)-f-binaphane B6 as the catalyst, [60]fullerene also reacted with allenoates at room temperature, providing a wide range of optically pure (S)-cyclopenteno[60]fullerenes in up to 99% ee (Scheme 8) [41]. This study

• provided a versatile and promising strategy for tailoring carbon materials (e.g., fullerenes, carbon nanotubes), imparting them with desired properties for applications in materials chemistry [42][43]. To further develop nucleophilic phosphine-catalyzed asymmetric reactions, Marinetti and co-workers

Carbon nanomaterials

• Anke Krueger

Beilstein J. Org. Chem. 2014, 10, 1785–1786, doi:10.3762/bjoc.10.186

• Keywords: carbon allotropes; carbon nanomaterials; carbon-rich molecules; The era of carbon nanomaterials has started with the first reports on fullerenes and related compounds in the mid-eighties, and a tremendous increase of the research activity in the field has been observed ever since. New classes of

• involving materials science, organic chemistry and physics. Synthetic organic chemistry is a major part of carbon materials chemistry as the rational synthesis of carbon allotropes such as fullerenes and nanotubes and related molecular compounds with and without heteroatoms remains a challenging task. The

• contribution does not end here but continues with the development of suitable reactions for the controlled functionalization of molecular as well as nanoscale allotropes such as fullerenes, diamondoids, carbon onions, carbynes or nanodiamonds. The interplay with knowledge gained by materials scientists and

Bis(β-lactosyl)-[60]fullerene as novel class of glycolipids useful for the detection and the decontamination of biological toxins of the Ricinus communis family

• Hirofumi Dohi,
• Takeru Kanazawa,
• Akihiro Saito,
• Keita Sato,
• Hirotaka Uzawa,
• Yasuo Seto and
• Yoshihiro Nishida

Beilstein J. Org. Chem. 2014, 10, 1504–1512, doi:10.3762/bjoc.10.155

• , Tsukuba, 305-8565, Japan 10.3762/bjoc.10.155 Abstract Glycosyl-[60]fullerenes were first used as decontaminants against ricin, a lactose recognition proteotoxin in the Ricinus communis family. A fullerene glycoconjugate carrying two lactose units was synthesized by a [3 + 2] cycloaddition reaction

• attempts of applying these glycomaterials for both the detection and the decontamination of biological toxins in an assumed polluted scene [19][20][21]. In the present study, we attempted to apply our N-glycosyl-[60]fullerenes [22][23][24][25], which were designed as a novel class of glycolipids with

• mono- and bis(α-D-mannopyranosyl)-[60]fullerenes in both AFM (atomic force microscopy) and DLS analyses. Probably, the smaller particles are bilayer vesicles that are stable in DMSO and pyridine while they can be destructed in parts by treatment with surfactants such as Triton-X [25]. These nano-sized

Homochiral BINOL-based macrocycles with π-electron-rich, electron-withdrawing or extended spacing units as receptors for C₆₀

• Marco Caricato,
• Silvia Díez González,
• Idoia Arandia Ariño and
• Dario Pasini

Beilstein J. Org. Chem. 2014, 10, 1308–1316, doi:10.3762/bjoc.10.132

• macrocycles [16], and urea-based structures [17] have all been exploited to develop the nanotube concept. Efficient supramolecular receptors for C60 and higher fullerenes have been already reported in the literature and research in this area is still very active [18][19]. Jasti and co-workers have

• made chiral by substituting one of the nitrogen atoms, and the enantioselective complexation of chiral higher fullerenes (C84) has been demonstrated [22]. Complexes of C60 and C70 with large, calix-type macrocycles formed by π-electron deficient pyridine aromatic rings bridged by a nitrogen heteroatom

• complexes in solution give insights into the role of nonspecific host–guest interactions (such as π–π stacking) for the overall stabilization of the complexes. We are currently designing binaphthyl-based hosts for the enantioselective recognition and separation of higher fullerenes and chiral nanotubes

Novel indolin-2-one-substituted methanofullerenes bearing long n-alkyl chains: synthesis and application in bulk-heterojunction solar cells

• Irina P. Romanova,
• Andrei V. Bogdanov,
• Inessa A. Izdelieva,
• Vasily A. Trukhanov,
• Gulnara R. Shaikhutdinova,
• Dmitry G. Yakhvarov,
• Shamil K. Latypov,
• Vladimir F. Mironov,
• Vladimir A. Dyakov,
• Ilya V. Golovnin,
• Dmitry Yu. Paraschuk and
• Oleg G. Sinyashin

Beilstein J. Org. Chem. 2014, 10, 1121–1128, doi:10.3762/bjoc.10.111

• crystalline domains. Moreover, the more soluble AIMs do not show a better miscibility with the P3HT crystalline phase. Keywords: bulk heterojunction; fullerenes; isatin; phosphorus; photovoltaics; Introduction Organic photovoltaics are a rapidly growing field of research due to its potential for production

Site-selective covalent functionalization at interior carbon atoms and on the rim of circumtrindene, a C₃₆H₁₂ open geodesic polyarene

• Hee Yeon Cho,
• Ronald B. M. Ansems and
• Lawrence T. Scott

Beilstein J. Org. Chem. 2014, 10, 956–968, doi:10.3762/bjoc.10.94

• ]. Whereas fullerenes comprising complete three-dimensional polyhedra can be classified as “closed” geodesic polyarenes, curved subunits of fullerenes are regarded as “open” geodesic polyarenes [4]. The fullerenes constitute one family of geodesic polyarenes, and bowl-shaped polycyclic aromatic hydrocarbons

• been developed in our laboratory and elsewhere [1][2][15][23][24][25][26][27]. In addition to synthesis, the functionalization of geodesic polyarenes – by both covalent and noncovalent bonding – has attracted significant attention in recent years. The functionalization of fullerenes was intensively

• explored immediately following the discovery of methods for bulk preparation of fullerenes in 1990 [28]. Within the first few years, several covalent functionalization sequences were introduced that became widely used for the construction of multifunctional architectures with C60 as an integral building

Thermodynamically stable [4 + 2] cycloadducts of lanthanum-encapsulated endohedral metallofullerenes

• Yuta Takano,
• Yuki Nagashima,
• M. Ángeles Herranz,
• Nazario Martín and
• Takeshi Akasaka

Beilstein J. Org. Chem. 2014, 10, 714–721, doi:10.3762/bjoc.10.65

• in situ from the sultine 4,5-benzo-3,6-dihydro-1,2-oxathiin 2-oxide and its derivative, to La metal-encapsulated fullerenes, La2@C80 or La@C82, afforded the novel derivatives of endohedral metallofullerenes (3a,b, 4a,b and 5b). Molecular structures of the resulting compounds were elucidated using

• ]. The encapsulation results in the electron transfer from metal atoms to the fullerene cage, which leads to unique electronic, magnetic, and chemical properties for EMFs that cannot be expected for empty fullerenes. Due to the numerous electronic properties EMFs are anticipated as promising materials in

• fullerenes simultaneously possess a low ionizing potential and a high electron affinity [1][2]. For mono-La endohedral fullerenes such as La@C82, the electron transfer results in paramagnetism of the fullerene cage [5]. The di-La endohedral fullerenes such as La2@C80 show diamagnetism [6]. This feature leads