Selective detection of DABCO using a supramolecular interconversion as fluorescence reporter

• Indrajit Paul,
• Debabrata Samanta,
• Sudhakar Gaikwad and
• Michael Schmittel

Beilstein J. Org. Chem. 2019, 15, 1371–1378, doi:10.3762/bjoc.15.137

• porphyrin edge capsules to cone-shaped inclusion complexes depending on the presence of C60/C70, however, a process that was not selective for one of the guests [24]. A spectacular case of guest sensing, but not guest-induced recognition, was demonstrated by Clever in a supramolecular cage-to-cage

Mechanochemical Friedel–Crafts acylations

• Mateja Đud,
• Anamarija Briš,
• Iva Jušinski,
• Davor Gracin and
• Davor Margetić

Beilstein J. Org. Chem. 2019, 15, 1313–1320, doi:10.3762/bjoc.15.130

• anthracene in 95% yield. This [4π + 4π] cycloreversion in mechanochemical conditions is analogous to previously described dissociation of labile anthracene/C60 cycloadduct [52]. When the reaction of 19 with 20 was carried out in solution (DCM, overnight), 60% of dimer was converted to anthracene, and traces

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

• there are not many spherical molecules known. Examples are the giant polyoxometalates reported by Müller et al. [3] and, more importantly for the current paper, fullerene C60. Because of the high symmetry of those compounds asymmetric modification is tedious with multiple synthesis and purification

• 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

• making it possible to obtain water soluble fullerenols as well as fullerenols that are still soluble in organic solvents [15][16][17][18][19]. The maximum number of OH groups, which could be attached to C60 is n = 44 [17]. Further derivatizations, where all hydroxy moieties of the compound have been

Mechanochemistry of supramolecules

• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2019, 15, 881–900, doi:10.3762/bjoc.15.86

• by NMR as well as other spectroscopic techniques. Georghiou et al. demonstrated the mechanochemical formation of a 1:1 supramolecular complex C60–tert-butylcalix[4]azulene 41 (Figure 23). The host–guest complexation was achieved by simple grinding the individual compounds in a mortar and pestle [95

• reaction through solid-state grinding. Hydrogen-bond donors are a) resorcinol and b) 1,8-dipyridylnaphthalene, respectively. Formation of the cage and encapsulation of [2.2]paracyclophane guest molecule in the cage was done simultaneously under mechanochemical conditions. Formation of the 1:1 complex C60

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

• introducing functional groups into the molecule directly. Among them, the formation of a 2:1 inclusion complex of γ-CD and C60 has been evaluated in various solvents such as water [21], toluene/water [22], DMSO [23], and DMF/water [24]. Although an impressive report that a 2:1 complex in water can be utilized

• as a homogeneous catalyst for nitrogen reduction under ambient conditions was published, the concentration of the complex in water is very low [25]. Thus, the development of γ-CD–C60 nonwovens by electrospinning might be useful as a novel inhomogeneous solid catalyst containing more C60. In this

• , isolation of fullerene by γ-CD motivated us to fabricate CD–fullerene inclusion complex fiber materials with molecularly dispersed fullerenes (Figure 1). Results and Discussion A representative example of a CD–fullerene inclusion complex is the combination of γ-CD and C60 [21][22][23][24]. Although the

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

• by Lash and Colby in their syntheses of 3 and 4. Although 5 was not sufficiently soluble in CS2, benzene, toluene or 1,2-dichlorobenzene to enable 1H NMR solution titration studies to be conducted with fullerene C60, a dilute solution of 5 in dichloromethane-d2 could be obtained that enabled its NMR

• constants. Conclusion Based upon the DFT calculations which we previously conducted in the solid-state study of 5 with C60, we postulated that due to the mechanochemical method of combining both components and the spherical nature of C60 that a possible interaction mode between host and guest could be as

Superstructures with cyclodextrins: Chemistry and applications IV

• Gerhard Wenz

Beilstein J. Org. Chem. 2017, 13, 2157–2159, doi:10.3762/bjoc.13.215

• , buckminsterfullerene C60 was covalently linked to two γ-CD rings [14]. This conjugate is highly soluble in water because it forms a sandwich-like self-complex, which makes it particularly useful as a sensitizer for singlet oxygen 1O2 generation [14]. Amphiphilic CD derivatives with oligoethylene oxide side chains form

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

• structure of dodecaacid C2 (Cn stands for Th symmetrical hexakisadducts C60{C[COO(CH2)n−1COOH]2}6, see Figure 1) revealing a complex hydrogen-bonding network in the crystalline state [57]. Based on this initial finding, we also utilized C2 and elongated derivative C3 as organic connectivity centers in metal

• detector using Cu Kα radiation (unsplit Kα1 + Kα2 doublet, mean wavelength λ = 154.19pm), reflection and transmission geometry. Hexakisadduct 2: C60 (565 mg, 785 µmol, 1 equiv), malonate 1 (3.10 g, 7.84 mmol, 10 equiv) and CBr4 (26.0 g, 78.4 mmol, 100 equiv) were dissolved in dry toluene (500 mL). DBU

• remove the solvent and traces of unreacted C60. After further column chromatographic separation (SiO2; toluene/ethyl acetate 10:1), pure hexakisadduct 2 (600 mg, 197 µmol, 25%) was obtained as a yellow crystalline solid. mp >200 °C dec; 1H NMR (400 MHz, CDCl3, rt) δ 1.44 (s, 108H, C(CH3)3), 1.99 (m, 3J

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

• fullerene bisadducts, specifically the C60 (IC60BA) and C70 (IC70BA) analogues (Figure 1), have been used successfully to boost the performance of poly(3-hexylthiopehene) (P3HT) based devices. The use of fullerene bisadducts improves the open circuit voltage of the device compared to mono-functionalized

Enabling technologies and green processes in cyclodextrin chemistry

• Giancarlo Cravotto,
• Marina Caporaso,
• Laszlo Jicsinszky and
• Katia Martina

Beilstein J. Org. Chem. 2016, 12, 278–294, doi:10.3762/bjoc.12.30

• derivatives by dissolving C60 in the amorphous powder obtained from the ball milled reactants and β-CD [90]. Another example that uses the energy transfer of ball milling is the preparation of MnBi/Fe-Co core/shell structured composites. However, no pure chemical reaction is used to prepare rare-earth free

Aggregation behaviour of amphiphilic cyclodextrins: the nucleation stage by atomistic molecular dynamics simulations

• Giuseppina Raffaini,
• Antonino Mazzaglia and
• Fabio Ganazzoli

Beilstein J. Org. Chem. 2015, 11, 2459–2473, doi:10.3762/bjoc.11.267

• preassembled state with the hydrophobic chains threading through one or two native CDs (see also the non-covalent super-amphiphilic complexes described in [33][34]), or of the unbiased aggregation process of two larger CDs encapsulating C60 [35]. Other studies considered again preassembled micelles, such as

Supramolecular chemistry: from aromatic foldamers to solution-phase supramolecular organic frameworks

• Zhan-Ting Li

Beilstein J. Org. Chem. 2015, 11, 2057–2071, doi:10.3762/bjoc.11.222

• ]. Thus, oligomers 13–15 may be considered as structural prototypes for creating new modifiable backbones. For example, porphyrin-appended U-shaped molecular tweezers 16 and 17 have been produced (Scheme 8). Compound 16 complexed C60 or C70 or their derivatives in chloroform or toluene through porphyrin

• –C60 stacking [35], while compound 17 strongly complexed 18 in the chloroform–acetonitrile binary medium [36] (Scheme 8). Because 18 could further form a threaded complex with 24-crown-8 19 driven by multiple O···H–N hydrogen bonds, the three components self-assembled into a unique dynamic [2]catenane

• compounds 12a–g and the formation of the helical conformation by the longer oligomers. The structures of compounds 13a,b, 14, and 15a–d. The structures of complex C60 16 and dynamic [2]catenane formed by compounds 17–19. The structure of homodimers 20a·20a and 20b·20b. The structures of foldamers 21 and

Polythiophene and oligothiophene systems modified by TTF electroactive units for organic electronics

• Alexander L. Kanibolotsky,
• Neil J. Findlay and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1749–1766, doi:10.3762/bjoc.11.191

• ) and BHJSCs. So far, various electroactive units have been anchored aside the polythiophene backbone, including ferrocene [8], porphyrin [9], 2-carboxyanthraquinone [10], 1,3-dithiole-2-ylidenefluorene [11][12], dithiinoquinoxaline [13][14] and fullerene C60 [15][16]. The incorporation of acceptor

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

• halide ions, 3 formed the C60 complex 5, in which C60 was bound within the bowl-like cup of the TTF-calix[4]pyrrole core in a ball-and-socket binding mode [43]. Recently, the C3-symmetric compounds 6a,b incorporating three TTF residues were reported by Amabilino, Avarvari, and co-workers (Figure 3) [21

• nanoobjects find functions in a variety of mass use devices. Radially expanded TTF oligomers 1 and 2a,b. TTF-calix[4]pyrrole 3 and its TNT and C60 complexes 4 and 5. C3-symmetric TTF derivatives 6a,b and 7a–c. Radially expanded TTF derivatives 8, 9, and 10a,b. Amphiphilic TTFs 11–14 and 15a,b. TTF dimers

Synthesis and spectroscopic properties of β-triazoloporphyrin–xanthone dyads

• Dileep Kumar Singh and
• Mahendra Nath

Beilstein J. Org. Chem. 2015, 11, 1434–1440, doi:10.3762/bjoc.11.155

• photoelectric materials [7][8]. In addition, porphyrins are potentially used as photosensitizers in photodynamic therapy to treat various types of tumors [9][10]. In recent years, many hybrid molecules including porphyrin–C60 [11], porphyrin–quinones [12] and porphyrin–cyclodextrin [13] conjugates were

Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F₄TCNQ

• Raúl García,
• M. Ángeles Herranz,
• Edmund Leary,
• M. Teresa González,
• Gabino Rubio Bollinger,
• Marius Bürkle,
• Linda A. Zotti,
• Yoshihiro Asai,
• Fabian Pauly,
• Juan Carlos Cuevas,
• Nicolás Agraït and
• Nazario Martín

Beilstein J. Org. Chem. 2015, 11, 1068–1078, doi:10.3762/bjoc.11.120

• upon oxidation has been skillfully used in a variety of D–π–A systems, namely exTTF–π-bridge–C60 derivatives, for determining the attenuation factor of the molecular wire (oligomer) acting as the π-bridge [20][21][22]. In this paper, we describe the synthesis of a new exTTF derivative, suitably

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

• through the sulfur bridges. The Ar-S-TTF molecules are size and shape matched for fullerenes (C60/C70), and the peripheral aryls show large rotational freedom that could adjust their spatial alignment to adapt to the environmental variations [61]. Regarding the structural feature of Ar-S-TTF, we have

• performed the complexation of Ar-S-TTFs with C60/C70, and found that Ar-S-TTF could form D–A type inclusion complexes with C60/C70 [63]. Crystallographic investigation reveals that the multidimensional interaction networks consisting of a central TTF core, peripheral aryls, and fullerenes are the key

• factors to stabilize the resulting supramolecular structures. Meanwhile, the solid state absorption study indicates that the inclusion complexes display a photoexcited electronic transition between Ar–S–TTF and C60/C70. To gain further insight into the structural features of Ar-S-TTF upon complexation

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

• and possible hydrophobic interactions was published in 2009 by Zhang et al. [37]. They compared the monovalent interaction of a porphyrin ligand to a C60 fullerene with the bivalent interaction of two ligands to one C60 (pincer complex) in aqueous environment. Thereby the rupture length decreased from

• 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

Design, synthesis and photochemical properties of the first examples of iminosugar clusters based on fluorescent cores

• Mathieu L. Lepage,
• Antoine Mirloup,
• Manon Ripoll,
• Fabien Stauffert,
• Anne Bodlenner,
• Raymond Ziessel and
• Philippe Compain

Beilstein J. Org. Chem. 2015, 11, 659–667, doi:10.3762/bjoc.11.74

• ][10]. From 2010, the field has however experienced a major take-off with the discovery of the first strong multivalent effects in glycosidase inhibition observed with DNJ clusters based on β-cyclodextrin or C60 cores showing strong affinity enhancements over the corresponding monomers (up to 610-fold

Synthesis of uniform cyclodextrin thioethers to transport hydrophobic drugs

• Lisa F. Becker,
• Dennis H. Schwarz and
• Gerhard Wenz

Beilstein J. Org. Chem. 2014, 10, 2920–2927, doi:10.3762/bjoc.10.310

• affinity towards rocuronium [24][25]. Furthermore, hydrophilic γ-CD thioethers show high affinities to other guests such as polycyclic aromatic hydrocarbons [26], botulin [27][28], and fullerene C60 [29]. Hydrophilic β-CD thioethers also tightly complex volatile benzene derivatives leading to a significant

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

• Diego Cortizo-Lacalle,
• Calvyn T. Howells,
• Upendra K. Pandey,
• Joseph Cameron,
• Neil J. Findlay,
• Anto Regis Inigo,
• Tell Tuttle,
• Peter J. Skabara and
• Ifor D. W. Samuel

Beilstein J. Org. Chem. 2014, 10, 2683–2695, doi:10.3762/bjoc.10.283

• the triads, theoretical DFT and TDDFT calculations were performed. Keywords: BODIPY; diketopyrrolopyrrole; organic semiconductors; organic solar cells; thiophene; Introduction The discovery of photoinduced electron transfer from conjugated polymers to fullerene (C60), and the favourable

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

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

• between C60 and the azide group in 6-azidohexyl β-lactoside per-O-acetate. A colloidal aqueous solution with brown color was prepared from deprotected bis(lactosyl)-C60 and was found stable for more than 6 months keeping its red color. Upon mixing with an aqueous solution of Ricinus communis agglutinin

• Discussion In our preceding studies [24][25], we have shown that bis(α-mannosyl)-[60]fullerene can be obtained by a coupling reaction between 1-azidoalkyl per-O-acetyl-glycoside and C60 together with [5,6]- and [6,6]-junction isomers of mono(α-mannosyl)-[60]fullerene. The bis(glycosyl)adduct is more polar

• than the two monoadducts and can be easily separated by silica gel column chromatography. Taking these preceding results into account, we prepared the bis(β-lactosyl)-[60]fullerene (bis-Lac-C60, Figure 1) in the present study. Synthesis of bis(per-O-acetyl-β-lactosyl)-[60]fullerene 4 The bis(lactosyl

Synthesis of the first examples of iminosugar clusters based on cyclopeptoid cores

• Mathieu L. Lepage,
• Alessandra Meli,
• Anne Bodlenner,
• Céline Tarnus,
• Francesco De Riccardis,
• Irene Izzo and
• Philippe Compain

Beilstein J. Org. Chem. 2014, 10, 1406–1412, doi:10.3762/bjoc.10.144

• inhibition [1][2], the pace of progress has been breath-taking with the discovery of iminosugar clusters showing outstanding affinity enhancements of up to four orders of magnitude over the parent monovalent analogues [3][4][5][6][7]. The best results were obtained with multivalent systems based on C60 [3

• ). These results may indicate that the ligand spatial presentation in cyclopeptoid-based iminosugars 10 is not optimal to achieve a substantial multivalent effect. It has been shown recently that the use of rigid scaffolds such as porphyrin or C60 could lead to large multivalent effects (up to 200-fold on

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

• cyclic adducts exhibit recognition properties towards C60 in toluene solutions (up to log Ka = 3.2) with variable stoichiometries and variable intensities of the charge-tranfer band upon complexation. Keywords: BINOL; C60; carbon nanomaterials; carbon nanostructures; chirality; macrocycles; sensors

• 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

• demonstrated how cyclo-p-phenylenes of suitable size are able to form very stable complexes with C60 [20]. Aida and co-workers have reported on π-electron rich, porphyrin-based cyclic structures, which are able to selectively recognize C60 [21]. In subsequent work, similar porphyrin-based systems have been