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

• , opening up supramolecular solid materials science and engineering. Keywords: cyclodextrin; electrospinning; fullerene; nanofiber; supramolecular complex; Introduction Fiber is a fundamental material that constitutes a variety of everyday items and supports the maintenance of life [1][2][3]. In the field

• paper, we report the successful electrospinning of native CD–fullerene inclusion complexes in a HFIP solution to produce a new type of supramolecular fiber material. An advantage of our system compared with the previous technique [10] is that only 12.5–20 w/v % CD/HFIP solution is required. This

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

Steric “attraction”: not by dispersion alone

• Ganna Gryn’ova and
• Clémence Corminboeuf

Beilstein J. Org. Chem. 2018, 14, 1482–1490, doi:10.3762/bjoc.14.125

• hydrocarbons has been emphasized by Sherrill et al. in 2009 [55]. Accordingly, several potentials with accurate electrostatics treatment have been developed and successfully applied to describe the intermolecular interactions of anthracene [56], polycyclic aromatic hydrocarbons [57][58][59][60] and fullerene

Recent advances on organic blue thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs)

• Thanh-Tuân Bui,
• Fabrice Goubard,
• Malika Ibrahim-Ouali,
• Didier Gigmes and
• Frédéric Dumur

Beilstein J. Org. Chem. 2018, 14, 282–308, doi:10.3762/bjoc.14.18

• since the first report mentioning their use as acceptors was published by Lee et al. in 2016 [62]. Prior to this work, phenoxaphosphine oxide derivatives were mostly studied for the design of flame-retardants [63] or as chiral molecules for fullerene recognition [64][65][66]. Similarly, the scope of

Synthesis and spectroscopic properties of β-meso directly linked porphyrin–corrole hybrid compounds

• Baris Temelli and
• Hilal Kalkan

Beilstein J. Org. Chem. 2018, 14, 187–193, doi:10.3762/bjoc.14.13

• obtaining multiporphyrin arrays [7][8][9] that could stabilize only metal ions in a bivalent state. To overcome this limitation, porphyrin conjugates with different chromophore groups such as fullerene [10][11][12], BODIPY [13][14][15], corrole [16][17][18][19][20][21][22][23], phthalocyanine [24][25][26

Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

• Satoru Mori and
• Norio Shibata

Beilstein J. Org. Chem. 2017, 13, 2273–2296, doi:10.3762/bjoc.13.224

• for the application in functional dyes with higher performance and in new industrial fields. An interesting example involves investigations on energy transfer between the phthalocyanine and the fullerene [101]. Normally, phthalocyanine plays the role as a donor type molecule in the field of organic

• semiconductors [102]. For example, a hybrid compound consisting of phthalocyanine and fullerene 20a causes the transfer of energy from the phthalocyanine unit to the fullerene unit when irradiated by light (Figure 6) [103][104]. However, such energy transfer does not occur in the hybrid of TFEO-ZnPc and

• fullerene 20b because the strong electron-withdrawing property of fluorine reverses the relationship between the electronic states of both units [105]. It was suggested that TFEO-Pc has an orbital energy closer to that of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) [106][107], which is a known

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

• , Germany 10.3762/bjoc.13.1 Abstract [60]Fullerene hexakisadducts possessing 12 carboxylic acid side chains form crystalline hydrogen-bonding frameworks in the solid state. Depending on the length of the linker between the reactive sites and the malonate units, the distance of the [60]fullerene nodes and

• strengthen the non-covalent interactions in a cooperative manner. In this regard, [60]fullerene hexakisadducts [47], which can arrange up to twelve functional sites with icosahedral symmetry, exhibit one of the highest degrees of functionalization for organic molecules (see Figure 1). In recent years, a

• variety of derivatives have been synthesized as spherical branching units [48][49][50][51][52][53] and, more recently, functionalized fullerene derivatives have been implemented into coordination compounds [54][55][56]. However, to the best of our knowledge, no fullerene-containing crystalline frameworks

Effects of solvent additive on “s-shaped” curves in solution-processed small molecule solar cells

• John A. Love,
• Shu-Hua Chou,
• Ye Huang,
• Guilllermo C. Bazan and
• Thuc-Quyen Nguyen

Beilstein J. Org. Chem. 2016, 12, 2543–2555, doi:10.3762/bjoc.12.249

• , resulting in a depth profile. To improve contrast between the two materials, deuterated fullerene PC61BM-d5 was used as a surrogate for PC71BM to establish a unique mass signal for the fullerene component [12][66][67]. Thus detection of deuterium in the mass spectrum implicitly signifies PC61BM-d5 in the

Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties

• Pierre Boufflet,
• Sebastian Wood,
• Jessica Wade,
• Zhuping Fei,
• Ji-Seon Kim and
• Martin Heeney

Beilstein J. Org. Chem. 2016, 12, 2150–2163, doi:10.3762/bjoc.12.205

• collection. With the thermal stability of all-polymer and polymer-fullerene blend microstructures being particularly problematic [19], block copolymers present a potential solution. Indeed, it has been shown that when block copolymers are used as additives in bulk heterojunction donor–acceptor blend layers

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

• Homoleptic zinc(II) complexes of di(phenylacetylene)azadipyrromethene (e.g., Zn(WS3)2) are potential non-fullerene electron acceptors for organic photovoltaics. To tune their properties, fluorination of Zn(WS3)2 at various positions was investigated. Three fluorinated azadipyrromethene-based ligands were

• absorber; non-fullerene acceptor; zinc(II) complex; Introduction Azadipyrromethenes (ADPs) (Figure 1a) are a class of monoanionic bidentate ligands with strong absorption in the visible and near IR range. Their absorbance and emission properties can be readily tuned through structural modifications and

Effect of the π-conjugation length on the properties and photovoltaic performance of A–π–D–π–A type oligothiophenes with a 4,8-bis(thienyl)benzo[1,2-b:4,5-b′]dithiophene core

• Ni Yin,
• Lilei Wang,
• Yi Lin,
• Jinduo Yi,
• Lingpeng Yan,
• Junyan Dou,
• Hai-Bo Yang,
• Xin Zhao and
• Chang-Qi Ma

Beilstein J. Org. Chem. 2016, 12, 1788–1797, doi:10.3762/bjoc.12.169

• fullerene derivative as the photoactive layer. This was ascribed to the influence of the orientation of the alkyl side chains. Although regioregular oligo(3-alkylthiophene)s are better building blocks for studying the effect of the π-conjugation length, only regioregular terthiophene (rr-3T) was reported to

Synthesis and characterization of benzodithiophene and benzotriazole-based polymers for photovoltaic applications

• Desta Gedefaw,
• Marta Tessarolo,
• Margherita Bolognesi,
• Mario Prosa,
• Renee Kroon,
• Wenliu Zhuang,
• Patrik Henriksson,
• Kim Bini,
• Ergang Wang,
• Michele Muccini,
• Mirko Seri and
• Mats R. Andersson

Beilstein J. Org. Chem. 2016, 12, 1629–1637, doi:10.3762/bjoc.12.160

• a blend of π-conjugated polymer (electron donor) and fullerene derivative (electron acceptor) sandwiched between two electrodes (anode and cathode) [1][2][3][4]. Noticeable achievements have been recorded in terms of the power conversion efficiency (PCE) of lab-scale single junction BHJ PSCs

Star-shaped and linear π-conjugated oligomers consisting of a tetrathienoanthracene core and multiple diketopyrrolopyrrole arms for organic solar cells

• Hideaki Komiyama,
• Chihaya Adachi and
• Takuma Yasuda

Beilstein J. Org. Chem. 2016, 12, 1459–1466, doi:10.3762/bjoc.12.142

• TTA-DPP2 with a fullerene derivative were evaluated by varying the thickness of the bulk heterojunction active layer. As a result of the enhanced visible absorption properties of the star-shaped π-conjugated structure, better photovoltaic performances were obtained with relatively thin active layers

• ability, and good miscibility with a fullerene derivative as an acceptor. Moreover, strong visible light photoabsorption ability for visible light is vital for the donor materials. Star-shaped molecules tethering multiple π-conjugated arms are capable of harvesting incident light effectively owing to

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

• separation; electron acceptor; fullerene bisadduct; organic solar cell; regioisomers; Introduction Organic solar cells (OSCs) are an emerging renewable energy technology that has achieved remarkable progress over the past two decades. Compared to traditional inorganic semiconductor solar cells, OSCs promise

• 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

• ). The α-bonds are the most reactive as they situated at the ends of the C70 molecule and therefore experience higher strain from the curvature of the molecule [10]. While reaction at non-[6,6]-bonds are possible, the thermodynamic products of fullerene adducts are usually located on the [6,6]-bonds [11

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

• in types 2) and 3) can reduce or eliminate the polluting environment. Reactions of type 1) are dominant in CD/BM literature; more than 98% of publications report the complexation of one or more components. Mechanochemistry opened a new synthetic pathway to the preparation of numerous fullerene

Exploring architectures displaying multimeric presentations of a trihydroxypiperidine iminosugar

• Camilla Matassini,
• Stefania Mirabella,
• Andrea Goti,
• Inmaculada Robina,
• Antonio J. Moreno-Vargas and
• Francesca Cardona

Beilstein J. Org. Chem. 2015, 11, 2631–2640, doi:10.3762/bjoc.11.282

• high multivalent effects towards jack-bean α-mannosidase were reported for fullerene- [11], cyclodextrin- [12][13] and porphyrin- [14] based scaffolds decorated with 1-deoxynojirimycin (DNJ) or 1-deoxymannojirimycin as the bioactive iminosugars. Self-assembled DNJ-based glycopeptides also experienced a

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

• . Under low temperature, this dynamic [2]catenane could be quantitatively generated. The intramolecular hydrogen bonds formed by the aromatic amide linkers remarkably enhanced the complexation of the porphyrin units towards the fullerene and the bipyridine ligand. Jiang further introduced amide subunits

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

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

• porphyrins with diverse functionalities such as quinolone [19], ferrocene [20], carbohydrate [21] and fullerene [22] through a copper(I)-catalyzed Huisgen–Sharpless–Meldal 1,3-dipolar cycloaddition reaction [23][24]. Some of these triazolo-bridged porphyrin dyads have shown an efficient intramolecular energy

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

• cyclized product. The cleavage of the acetate groups with sodium methoxide in methanol gave the glycophane (a glycophane is a hybrid of carbohydrate and cyclophane) 143 (27%, Scheme 21). The synthesis of fullerene-related molecules with high binding affinity and/or high selectivity is an active research

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

• co-crystals of fullerene (as the acceptor) and arylthio-substituted tetrathiafulvalene derivatives (Ar-S-TTF, as the donor) were prepared and their structural features were thoroughly investigated. The formation of co-crystals relies on the flexibility of Ar-S-TTF and the size matches between Ar-S

• -TTF and fullerene. Regarding their compositions, the studied co-crystals can be divided into two types, where types I and II have donor:acceptor ratios of 1:1 and 1:2, respectively. Multiple intermolecular interactions are observed between the donor and acceptor, which act to stabilize the structures

• of the resulting co-crystals. In the type I co-crystals, the fullerene molecule is surrounded by four Ar-S-TTF molecules, that is, two Ar-S-TTF molecules form a sandwich structure with one fullerene molecule and the other two Ar-S-TTF molecules interact with the fullerene molecule along their lateral

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

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

• interpenetrating network they form within a bulk heterojunction (BHJ), has led to intense research directed towards the synthesis of conjugated polymers for bulk heterojunction organic photovoltaics (OPVs) [1][2][3]. In these devices, the conjugated polymer acts as an electron donor and a soluble fullerene, most

• results [26][27][28]. A PCE greater than 4% was achieved in combination with phenyl-C71-butyric acid methyl ester (PC71BM) [29]. Interestingly, a small molecule based on a DPP core substituted with electron-withdrawing units was also used as an acceptor in OPVs as a substitute for fullerene with PCEs of 1

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