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Search for "fullerene" in Full Text gives 75 result(s) in Beilstein Journal of Organic Chemistry.
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
- quantified by means of sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), and the results were discussed in terms of detection and decontamination of the deadly biological toxin in the Ricinus communis family. Keywords: fullerene; multivalent glycosystems; oligosaccharides; proteotoxins
- notable biological and physical properties. For example, bis(α-D-mannopyranosyl)-[60]fullerene is capable of forming a liposome-like supramolecule in aqueous media and exhibits a strong binding activity to an α-mannose-binding lectin (concanavalin A, Con A) as the result not only of carbohydrate cluster
Graphical Abstract
Figure 1: Structure of bis(β-lactosyl)-[60]fullerene (bis-Lac-C60).
Scheme 1: Synthesis of bis-Lac-C60. Reagents and conditions: (a) 6-chloro-1-hexanol, TMSOTf, CH2Cl2, −40 °C, ...
Figure 2: Precipitation assay of bis-Lac-C60 colloidal solution. The tubes were allowed to stand for 10 min a...
Figure 3: Schematic image for the quantitative analysis of ricin protein in the colloidal suspension of bis-L...
Figure 4: A modified procedure for the rapid detection and the efficient decontamination of ricin and ricin-l...
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
- 119991, Russian Federation 10.3762/bjoc.10.111 Abstract An easy, high-yield and atom-economic procedure of a C60 fullerene modification using a reaction of fullerene C60 with N-alkylisatins in the presence of tris(diethylamino)phosphine to form novel long-chain alkylindolinone-substituted
- of low-cost and flexible solar cells [1][2][3]. Organic solar cells are mainly based on bulk heterojunctions composed of a polymer donor and a fullerene acceptor. A number of promising donor materials has been developed, whereas very few successful fullerene derivatives have been proposed. The most
- popular fullerene derivative in organic photovotaics is (PCBM) [4][5][6]. As an alternative to PCBM, we recently suggested indolinone-substituted methanofullerenes (IM) [7]. The principal advantages of IM are their easier synthesis and purification as compared to PCBM [7][8]. Indeed, the IM can be
Graphical Abstract
Figure 1: Structures of the indolinone-substituted methanofullerenes prepared earlier.
Scheme 1: The two-step synthetic pathway towards the methanofullerenes AIM 1–9.
Figure 2: Optical absorption spectra of AIM 9, PCBM, and C60 in CH2Cl2 (2·10−5 mol·L−1, the cell thickness d ...
Figure 3: Cyclic voltammetry curve of AIM 9.
Figure 4: J–V characteristics of P3HT/AIMs and reference P3HT/PCBM devices for the P3HT/fullerene weight rati...
Figure 5: Absorption spectra of P3HT/fullerene blended films. The P3HT/PCBM blend was annealed during 15 min ...
Figure 6: AFM topography image of an as-casted 1:1 P3HT:AIM 7 blended film.
The Ugi four-component reaction as a concise modular synthetic tool for photo-induced electron transfer donor-anthraquinone dyads
- Sarah Bay,
- Gamall Makhloufi,
- Christoph Janiak and
- Thomas J. J. Müller
Beilstein J. Org. Chem. 2014, 10, 1006–1016, doi:10.3762/bjoc.10.100
- moieties C60 fullerene [43][44][45], and quinones, such as 9,10-anthraquinone as a potential two electron acceptor, have been commonly used in Do–Acc arrangements [46][47][48][49][50][51]. In previous studies phenothiazine–anthraquinone couples have been introduced into peptide scaffolds [52][53][54] and
Graphical Abstract
Figure 1: Phenothiazine–anthraquinone dyad 1, donor-only (2) and acceptor-only (3) models assembled by Ugi 4C...
Scheme 1: Ugi 4CR synthesis of donor–anthraquinone dyads 8.
Scheme 2: Ugi 4CR synthesis of donor-only reference systems 10.
Figure 2: Molecular structure of S(O)-1 (left) (30% ellipsoids, except for the CH3CH2 end of the hexyl group,...
Figure 3: Cyclic voltammogram of dyad 8c (recorded in CH2Cl2, T = 298 K, c (8c) = 0.1 mol·L−1, Pt working ele...
Figure 4: DFT-computed (B3LYP, 6-311G*) frontier molecular orbitals HOMO (bottom) and LUMO (top) of the pheno...
Figure 5: Normalized absorption spectra of the phenothiazine–anthraquinone dyad 8c (recorded in CH2Cl2, c (8c...
Figure 6: Absorption spectra of Do–anthraquinone dyads 8c (top) and 8e (bottom) with the corresponding refere...
Figure 7: Normalized absorption and emission spectra of Ugi-donor compounds 2 and 10 (recorded in CH2Cl2, T =...
Figure 8: Emission spectra of donor-only system 2 phenothiazine–anthraquinone dyads 8a,b (top), and the donor...
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
- Hee Yeon Cho Ronald B. M. Ansems Lawrence T. Scott Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467-3860, USA 10.3762/bjoc.10.94 Abstract Circumtrindene (6, C36H12), one of the largest open geodesic polyarenes ever reported, exhibits fullerene
- -like reactivity at its interior carbon atoms, whereas its edge carbons react like those of planar polycyclic aromatic hydrocarbons (PAHs). The Bingel–Hirsch and Prato reactions – two traditional methods for fullerene functionalization – afford derivatives of circumtrindene with one of the interior 6:6
- lowering of the energy of the LUMO, while leaving the energy or the HOMO relatively unchanged. Considerable effort by a number of research groups has been devoted to the preparation of fullerene fragments and to studies of their chemical and physical properties [6][7][8][9]. Several laboratories, including
Graphical Abstract
Figure 1: Prototypical open and closed geodesic polyarenes.
Figure 2: Planar vs pyramidalized π-system.
Figure 3: Selected examples of geodesic polyarenes synthesized by FVP.
Scheme 1: Covalent functionalization of fullerene C60 by the Bingel–Hirsch reaction and the Prato reaction.
Scheme 2: Fullerene-type chemistry at interior carbon atoms of corannulene (1) and diindenochrysene (10).
Figure 4: POAV angles of fullerene C60 (2), corannulene (1), and diindenochrysene (10).
Scheme 3: Synthesis of circumtrindene (6) by FVP.
Scheme 4: Synthetic route to 3,9,15-trichlorodecacyclene (12).
Figure 5: POAV angle and bond lengths of circumtrindene.
Scheme 5: Bingel–Hirsch reaction of circumtrindene (6).
Scheme 6: Proposed mechanism for the Bingel–Hirsch reaction of circumtrindene (6).
Scheme 7: Prato reaction of circumtrindene (6).
Figure 6: LUMO orbital map of circumtrindene (B3LYP/6-31G*). The darkest blue areas correspond to the regions...
Figure 7: Electrostatic potentials on the surfaces of circumtrindene (B3LPY/6-31G*).
Figure 8: Monoindeno- (25), diindeno- (26), and triindenocircumtrindene (27).
Figure 9: Two different types of rim carbon atoms on circumtrindene.
Scheme 8: Site-selective peripheral monobromination of circumtrindene.
Scheme 9: Suzuki coupling and ring-closing reactions toward indenocircumtrindene (25).
Scheme 10: Suzuki coupling to prepare compound 30.
Figure 10: Chemical shifts of ortho-methyl groups in 30 and 31.
Unusual polymorphism in new bent-shaped liquid crystals based on biphenyl as a central molecular core
- Anna Kovářová,
- Svatopluk Světlík,
- Václav Kozmík,
- Jiří Svoboda,
- Vladimíra Novotná,
- Damian Pociecha,
- Ewa Gorecka and
- Natalia Podoliak
Beilstein J. Org. Chem. 2014, 10, 794–807, doi:10.3762/bjoc.10.75
- ], semifluorinated alkyl chains [14][20], and fullerene [21] into the terminal chain(s), variation of the linkage groups [10][22][23][24] (ester, azo, azoxy, imine, H-bond, cinnamoyl). Also dimeric, dendritic, and polymeric liquid crystals possessing the biphenyl moiety in the centre of the bent mesogenic unit were
Graphical Abstract
Figure 1: Structure of the central cores and lengthening arms.
Scheme 1: Synthesis of compounds of series I–III.
Scheme 2: Synthesis of compounds of series IV–VI.
Figure 2: Chemical formulae of studied compounds I–VI.
Figure 3: DSC plots for compounds a) IIb, b) IVb and c) Vb taken on second heating (upper curve) and cooling ...
Figure 4: Planar texture of Ib in the SmCAPA phase at temperature T = 130 °C (a) without field, and (b) in th...
Figure 5: Planar texture of IIb (a) at the phase transition from the SmAP (upper right corner) to the SmCAPA ...
Figure 6: Switching current for compound IIb at T = 150 °C, taken in the SmCAPA phase at a triangular field, E...
Figure 7: Planar texture of IIb compound the SmCSPA phase at T = 130 °C, (a) without applied field and (b) in...
Figure 8: Temperature dependence of the layer spacing value, d, and intensity of the corresponding X-ray sign...
Figure 9: X-ray patterns of a partially aligned sample of IIb in (a) the SmCG phase at 148 °C and (b) in the ...
Figure 10: 3-Dimensional plot of the imaginary part of permittivity, ε’’, versus temperature and frequency for ...
Figure 11: Temperature dependence of the dielectric strength, Δε, and relaxation frequency, fr, for IIb.
Figure 12: Schematic organization of bent-shaped molecules in layers for the SmCAPA–SmCG–SmCSPA sequence of me...
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
- ]. 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
- various fields such as chemistry, biology, and material science. Among various kinds of EMFs, those encapsulating La atoms are especially attractive molecules because of their electronic and magnetic characteristics. As a result of the three electron transfer per La atom to the fullerene cage, the
- 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
Graphical Abstract
Scheme 1: Synthesis of [4 + 2] adducts of La2@C80.
Figure 1: HPLC profiles of the reaction solutions (black) before and (red) after the reaction of La2@C80 and ...
Figure 2: MALDI–TOF mass (negative mode) spectra of (a) 3b and (b) 4b, using 1,1,4,4-tetraphenyl-1,3-butadien...
Figure 3: UV–vis/near-IR absorption spectra of 3b and 4b recorded by the diode array detector of the HPLC app...
Figure 4: MALDI–TOF mass spectrum (negative mode) of the reaction mixture from La2@C80 and 1a, using 1,1,4,4-...
Figure 5: 1H NMR spectra of (a) the mixture of 3a and 4a in C2D2Cl4 at 248 K, and (b) isolated 4a at 230 K, r...
Figure 6: HPLC profiles of the mixture of 3a and 4a, (a) after heating in refluxing 1,2-dichlorobenzene and (...
Figure 7: HPLC profiles of the reaction mixture of 3b and 4b, (black) before and (red) after heating in reflu...
Figure 8: UV–vis/near-IR absorption spectra of 3b and 4a in toluene.
Figure 9: Temperature-dependent 1H NMR spectra of 4a in C2D2Cl4 (left) at 300 MHz, and (right) at 500 MHz for...
Scheme 2: Synthesis of [4 + 2] adducts of La@C82.
Figure 10: HPLC profiles of the reaction mixture for 5b. Conditions: column, Buckyprep (Ø 4.6 mm × 250 mm); el...
Figure 11: MALDI–TOF mass spectra (negative mode) of 5b, using 1,1,4,4-tetraphenyl-1,3-butadiene as matrix.
Figure 12: Vis–near-IR spectra of 5b, 6 and La@C82 in CS2.
Figure 13: 1H NMR spectrum of [5b]− in acetone-d6/CS2 (3/1 = v/v) at 223 K.
Figure 14: 13C NMR spectrum of [5b]− in acetone-d6/CS2 (3/1 = v/v).
Figure 15: HPLC profiles for comparison of the thermal stabilities of (a) 5b and (b) 6 at 30 °C. Conditions: c...
Tuning the interactions between electron spins in fullerene-based triad systems
- Maria A. Lebedeva,
- Thomas W. Chamberlain,
- E. Stephen Davies,
- Bradley E. Thomas,
- Martin Schröder and
- Andrei N. Khlobystov
Beilstein J. Org. Chem. 2014, 10, 332–343, doi:10.3762/bjoc.10.31
- 10.3762/bjoc.10.31 Abstract A series of six fullerene–linker–fullerene triads have been prepared by the stepwise addition of the fullerene cages to bridging moieties thus allowing the systematic variation of fullerene cage (C60 or C70) and linker (oxalate, acetate or terephthalate) and enabling precise
- control over the inter-fullerene separation. The fullerene triads exhibit good solubility in common organic solvents, have linear geometries and are diastereomerically pure. Cyclic voltammetric measurements demonstrate the excellent electron accepting capacity of all triads, with up to 6 electrons taken
- up per molecule in the potential range between −2.3 and 0.2 V (vs Fc+/Fc). No significant electronic interactions between fullerene cages are observed in the ground state indicating that the individual properties of each C60 or C70 cage are retained within the triads. The electron–electron
Graphical Abstract
Figure 1: Structures of triads 1–6 and precursor molecules 7–8 used for the synthesis of the asymmetric syste...
Scheme 1: The one-step synthetic procedure towards the oxalate-bridged fullerene triads 4 and 6.
Scheme 2: Attempted synthetic pathway towards the formation of the C60–C70 oxalate bridged fullerene triad al...
Scheme 3: Synthetic pathway to the asymmetric fullerene triad 5 allowing introduction of the fullerene cages ...
Figure 2: Cyclic voltammograms of the terephthalate bridged triads 1–3 (left) and oxalate bridged triads 4–6 ...
Figure 3: Fluid solution EPR spectra recorded at 297 K for the two electron reduced species of compounds 1 an...
Figure 4: Frozen solution EPR spectra of triads 42− (a) and 12− (c), prepared by two electron reduction of 4 ...
Controlled synthesis of poly(3-hexylthiophene) in continuous flow
- Helga Seyler,
- Jegadesan Subbiah,
- David J. Jones,
- Andrew B. Holmes and
- Wallace W. H. Wong
Beilstein J. Org. Chem. 2013, 9, 1492–1500, doi:10.3762/bjoc.9.170
- mixing of reagents, boosting reaction rates, and safe handling of reactive intermediates. Using a commercial continuous-flow tube reactor [19], we have already demonstrated multigram synthesis of fullerene derivatives by cycloaddition reactions [11] as well as rapid conjugated-polymer synthesis using
Graphical Abstract
Scheme 1: (a) Preparation of thiophene Grignard monomer and synthesis of P3HT by Kumada catalyst transfer pol...
Figure 1: Plot of number-average molecular weight, Mn, versus monomer–catalyst ratio [M]0/[I]0 for batch and ...
Figure 2: MALDI mass spectrum of low-molecular-weight preparation (GPC, Mn = 6.2 kg/mol) of P3HT in continuou...
Figure 3: Plot of number-average molecular weight, Mn, versus monomer–catalyst ratio [M]0/[I]0 for batch and ...
Scheme 2: Schematic representation of the telescoped preparation of P3HT in a flow reactor.
Figure 4: 1H NMR (CDCl3, 500 MHz) spectra of P3HT samples prepared in (a) flow and (b) batch show comparable ...
Figure 5: (a) Schematic diagram of the photovoltaic device geometry and (b) J–V curves of BHJ solar cells wit...
A study on electrospray mass spectrometry of fullerenol C60(OH)24
- Mihaela Silion,
- Andrei Dascalu,
- Mariana Pinteala,
- Bogdan C. Simionescu and
- Cezar Ungurenasu
Beilstein J. Org. Chem. 2013, 9, 1285–1295, doi:10.3762/bjoc.9.145
- anions formed by electron addition to a fullerenyl radical shall be described as fullerene carbanions and referred to as fullerenide anions (M3 in Scheme 1) and [mM + ne]m–n∙ shall be described as molecular anions. As regards to the observation of distonic fullerenyl-fullerenate M7 ions, such distonic
- on pristine fullerene anion radicals [34][35][36][37] unquestionably confirmed their generation by electron transfer from various electron donors (aliphatic and aromatic amines especially) [38][39], one can postulate that, under ESI conditions, a distonic radical carbanion [(C60(OH)24−•)2]2−• is
- first generated by electron transfer from H2N− produced by ammonia ionization and then undergoes consecutive OH radical losses and electron redistribution until the entire reconstruction of the electronic structure of pristine fullerene is achieved. Positive-ionization-mode mass spectra In Figure 3 are
Graphical Abstract
Scheme 1: Proposed mechanisms for the formation of fullerenol anions and distonic radical anions observed by ...
Figure 1: Negative-ion mass spectra for a 0.5 × 10−5 M solution of C60(OH)24 in ultrapure water: (a) full sca...
Scheme 2: Examples of proposed structures for the main deprotonated molecules and final distonic molecular io...
Scheme 3: Proposed (−)ESI-MS ionization mechanisms for fullerenol C60(OH)24 in pure water.
Figure 2: Negative-ion mass spectra of a 0.5 × 10−5 M aqueous solution of C60(OH)24 in ammonia solution: (a) ...
Figure 3: Positive ionization ESI mass spectrum of C60(OH)24 in (a) 3 × 10−1 M (b) 2 × 10−2 M aqueous ammonia...
Scheme 4: Proposed (+)ESI-MS ionization mechanisms for fullerenol C60(OH)24 in ammonia solution.
Incorporation of perfluorohexyl-functionalised thiophenes into oligofluorene-truxenes: synthesis and physical properties
- Neil Thomson,
- Alexander L. Kanibolotsky,
- Joseph Cameron,
- Tell Tuttle,
- Neil J. Findlay and
- Peter J. Skabara
Beilstein J. Org. Chem. 2013, 9, 1243–1251, doi:10.3762/bjoc.9.141
- such as fullerene fragments [4] and liquid-crystalline compounds [5]. Positions C5, C10 and C15 can be functionalised with a range of substituents, commonly saturated alkyl chains, which can enhance the solubility and processability as well as reduce intermolecular π–π stacking [6], but there are also
Graphical Abstract
Figure 1: Labelled truxene and compounds T1 and T4.
Scheme 1: Synthesis of the thiophene-fluorene arm for the 3-isomer.
Scheme 2: Synthesis of the thiophene-fluorene arm for the 4-isomer.
Scheme 3: Coupling of arms to the truxene core.
Scheme 4: Synthesis of T4-4FTh.
Figure 2: Normalised absorbance (solid) and emission (dashed) of materials in solution (dichloromethane).
Figure 3: HOMO−1 (bottom, left), HOMO (bottom, right), LUMO (top, left) and LUMO+1 (top, right) of T1-3FTh.
Figure 4: HOMO−1 (bottom, left), HOMO (bottom, right), LUMO (top, left) and LUMO+1 (top, right) of T1-4FTh.
Enhancement of efficiency in organic photovoltaic devices containing self-complementary hydrogen-bonding domains
- Rohan J. Kumar,
- Jegadesan Subbiah and
- Andrew B. Holmes
Beilstein J. Org. Chem. 2013, 9, 1102–1110, doi:10.3762/bjoc.9.122
- -processing, leading to cost and energy input advantages in device manufacture. Recently, a donor–acceptor small molecule with a cyanopyridone moiety as the acceptor motif and displaying moderate photovoltaic efficiency in a BHJ device with a fullerene was reported [20]. The efficiency of these optimized
- reported for compound 1 [20] and are suitable for charge transfer to take place to fullerene-based electron acceptors, such as PC61BM. The NH cyanopyridone unit can presumably exist as a number of tautomers; however, if present, these do not appear to affect the electronic properties in solution
Graphical Abstract
Figure 1: N-ethylhexyl-substituted (1) [20] and target free N–H (2) cyanopyridone structures.
Scheme 1: Synthesis of the cyanopyridone 2, reagents and conditions: (i) Pd(PPh3)4, Cs2CO3, toluene, reflux, ...
Figure 2: (a) Chloroform (solid line) and thin-film (dashed line) UV–vis absorption and emission spectra and ...
Figure 3: The concentration dependence of (a) the NH 1H NMR chemical shift and (b) the vinyl proton chemical ...
Figure 4: AFM height image of observed nanostructures of films drop cast from (a) 10 mg/mL and (b) 1 mg/mL ch...
Figure 5: Dimeric structures of 2. (a) centrosymmetric dimer of 2; (b) bond-rotated centrosymmetric dimer of 2...
Figure 6: Schematic representation of self-complementary interactions leading to one-dimensional chains.
Flow photochemistry: Old light through new windows
- Jonathan P. Knowles,
- Luke D. Elliott and
- Kevin I. Booker-Milburn
Beilstein J. Org. Chem. 2012, 8, 2025–2052, doi:10.3762/bjoc.8.229
- degradations, dual-channel reactors have been used for synthetically useful transformations. Returning to the oxidation of α-terpinene, moderate yields of ascaridole were obtained by using a silica-supported fullerene promoter [38]. Similarly, L-methionine was efficiently oxidised to the corresponding
Graphical Abstract
Figure 1: An immersion-well batch reactor with 125 W medium pressure Hg lamp.
Figure 2: Transmission profile of a 0.05 M solution, ε = 200 M−1 cm−1.
Figure 3: Schematic of a typical microflow photochemical reactor (above) and detail of a triple-channel micro...
Figure 4: Schematic of a typical macroflow photochemical reactor (above) and images of the FEP photochemical ...
Scheme 1: [2 + 2] photocycloadditions of enones with enol derivatives.
Scheme 2: Competing reactions in an intramolecular [2 + 2] photocycloaddition.
Scheme 3: Diastereocontrolled cycloaddition of a cyclic enone with cyclopentene.
Scheme 4: Comparison of yields and reaction times for a batch reactor with a microflow system.
Scheme 5: Intramolecular [2 + 2] photocycloaddition.
Scheme 6: Paterno–Büchi reaction of benzophenone with an allylic alcohol.
Scheme 7: Photooxygenation of cyclopentadiene.
Scheme 8: Preparation of the anthelmintic ascaridole 23.
Scheme 9: Production of rose oxide 27 from (−)-β-citronellol (24).
Scheme 10: Photocatalytic alkylation of benzylamine.
Scheme 11: Photocatalytic reduction of 4-nitroacetophenone.
Scheme 12: Conversion of L-lysine to L-pipecolinic acid.
Scheme 13: Photocatalytic hydrodehalogenation.
Scheme 14: Photocatalytic aza-Henry reactions.
Scheme 15: Photocatalytic α-alkylation of aliphatic ketones.
Scheme 16: Decarboxylative photochemical additions.
Scheme 17: Photochemical addition of isopropanol to furanones.
Scheme 18: Photochemical addition of methanol to limonene.
Scheme 19: Light-promoted reduction of flavone.
Scheme 20: Photoreduction of benzophenone with benzhydrol.
Scheme 21: Barton reaction in a microflow system.
Scheme 22: Microflow synthesis of vitamin D3.
Scheme 23: photochemical chlorination of cyclohexane.
Scheme 24: photochemical cyanation of pyrene.
Scheme 25: Intermolecular [2 + 2] cycloaddition of maleimide (76) and intramolecular [2 + 2] cycloaddition of ...
Scheme 26: Intramolecular [5 + 2] cycloaddition of maleimide under flow conditions.
Scheme 27: Intramolecular [5 + 2] cycloaddition as a key step in the synthesis of (±)-neostenine.
Scheme 28: In situ generation of a thioaldehyde by photolysis of a phenacyl sulfide.
Scheme 29: Photodimerisation of maleic anhydride.
Scheme 30: [2 + 2] cycloaddition of a chiral enone with ethylene.
Scheme 31: Intramolecular [2 + 2] cycloaddition of a cyclopentenone.
Scheme 32: Photochemical Wolff rearrangement and cyclisation to β-lactams.
Scheme 33: Photochemical rearrangement of aryl azides.
Scheme 34: Rearrangement of quinoline N-oxides to quinolones.
Scheme 35: Photochemical rearrangement of cyclobutenones.
Scheme 36: Photoisomerisation en route to a vitamin-D derivative.
Scheme 37: Schematic of the Seeberger photooxygenation apparatus and sensitised photooxygenation of citronello...
Scheme 38: Sensitised photooxygenation of dihydroartemisinic acid.
Scheme 39: Photochemical preparation of CpRu(MeCN)3PF6.
Scheme 40: In situ photochemical generation and reaction of a [CpRu]+ catalyst.
Scheme 41: Intermolecular alkene–alkyne coupling with photogenerated catalyst.
Scheme 42: PET deoxygenation of nucleosides.
Scheme 43: Photochemical defluorination of DABFT.
Scheme 44: Aromatic azide reduction by visible-light-mediated photocatalysis.
Scheme 45: Examples of visible-light-mediated reactions.
Scheme 46: Visible-light-mediated formation of iminium ions.
Scheme 47: Examples of visible-light-mediated photocatalytic reactions.
Scheme 48: Anhydride formation from a visible-light-mediated process.
Scheme 49: Light-mediated conjugate addition of glycosyl bromide 141 to acrolein.
Scheme 50: Visible-light-mediated photocyclisation to [5]helicene.
The chemistry of bisallenes
- Henning Hopf and
- Georgios Markopoulos
Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225
- . Derivative 150 can be desilylated to a C60H36 hydrocarbon, whose C36 backbone represents ca. 60% of the fullerene framework and which can be mapped onto C60 [121]. A pericyclic reaction of conjugated bisallenes which has also been studied extensively over the years involves the Diels–Alder addition with both
Graphical Abstract
Figure 1: Loschmidt’s structure proposal for benzene (1) (Scheme 181 from [3]) and the corresponding modern stru...
Figure 2: The first isolated bisallenes.
Figure 3: Carbon skeletons of selected bisallenes discussed in this review.
Scheme 1: The preparation of 1,2,4,5-hexatetraene (2).
Scheme 2: The preparation of a conjugated bisallene by the DMS-protocol.
Scheme 3: Preparation of the 3-deuterio- and 3,4-dideuterio derivatives of 24.
Scheme 4: A versatile method to prepare alkylated conjugated bisallenes and other allenes.
Scheme 5: A preparation of 3,4-dimethyl-1,2,4,5-hexatetraene (38).
Scheme 6: A (C6 + 0)-approach to 1,2,4,5-hexatetraene (2).
Scheme 7: The preparation of a fully alkylated bisallenes from a 2,4-hexadiyne-1,6-diol diacetate.
Scheme 8: The preparation of the first phenyl-substituted conjugated bisallenes 3 and 4.
Scheme 9: Selective hydrogenation of [5]cumulenes to conjugated bisallenes: another (C6 + 0)-route.
Scheme 10: Aryl-substituted conjugated bisallenes by a (C3 + C3)-approach.
Scheme 11: Hexaphenyl-1,2,4,5-hexatetraene (59) by a (C3 + C3)-approach.
Scheme 12: An allenation route to conjugated bisallenes.
Scheme 13: The preparation of 3,4-difunctionalized conjugated bisallenes.
Scheme 14: Problems during the preparation of sulfur-substituted conjugated bisallenes.
Scheme 15: The preparation of 3,4-dibromo bisallenes.
Scheme 16: Generation of allenolates by an oxy-Cope rearrangement.
Scheme 17: A linear trimerization of alkynes to conjugated bisallenes: a (C2 + C2 + C2)-protocol.
Scheme 18: Preparation of a TMS-substituted conjugated bisallene by a C3-dimerization route.
Scheme 19: A bis(trimethylsilyl)bisallene by a C3-coupling protocol.
Scheme 20: The rearrangement of highly substituted benzene derivatives into their conjugated bisallenic isomer...
Scheme 21: From fully substituted benzene derivatives to fully substituted bisallenes.
Scheme 22: From a bicyclopropenyl to a conjugated bisallene derivative.
Scheme 23: The conversion of a bismethylenecyclobutene into a conjugated bisallene.
Scheme 24: The preparation of monofunctionalized bisallenes.
Scheme 25: Preparation of bisallene diols and their cyclization to dihydrofurans.
Scheme 26: A 3,4-difunctionalized conjugated bisallene by a C3-coupling process.
Scheme 27: Preparation of a bisallenic diketone by a coupling reaction.
Scheme 28: Sulfur and selenium-substituted bisallenes by a [2.3]sigmatropic rearrangement.
Scheme 29: The biallenylation of azetidinones.
Scheme 30: The preparation of a fully ferrocenylated conjugated bisallene.
Scheme 31: The first isomerization of a 1,5-hexadiyne to a 1,2,4,5-hexatetraene.
Scheme 32: The preparation of alkynyl-substituted bisallenes by a C3-dimerization protocol.
Scheme 33: Preparation of another completely ferrocenylated bisallene.
Scheme 34: The cyclization of 1,5-hexadiyne (129) to 3,4-bismethylenecyclobutene (130) via 1,2,4,5-hexatetraen...
Scheme 35: Stereochemistry of the thermal cyclization of bisallenes to bismethylenecyclobutenes.
Scheme 36: Bisallene→bismethylenecyclobutene ring closures in the solid state.
Scheme 37: A bisallene cyclization/dimerization reaction.
Scheme 38: A selection of Diels–Alder additions of 1,2,4,5-hexatetraene with various double-bond dienophiles.
Scheme 39: The stereochemistry of the [2 + 4] cycloaddition to conjugated bisallenes.
Scheme 40: Preparation of azetidinone derivatives from conjugated bisallenes.
Scheme 41: Cycloaddition of heterodienophiles to a conjugated bisallene.
Scheme 42: Addition of triple-bond dienophiles to conjugated bisallenes.
Scheme 43: Sulfur dioxide addition to conjugated bisallenes.
Scheme 44: The addition of a germylene to a conjugated bisallene.
Scheme 45: Trapping of conjugated bisallenes with phosphinidenes.
Scheme 46: The cyclopropanantion of 1,2,4,5-hexatetraene (2).
Scheme 47: Photochemical reactions involving conjugated bisallenes.
Scheme 48: Base-catalyzed isomerizations of conjugated bisallenes.
Scheme 49: Ionic additions to a conjugated bisallene.
Scheme 50: Oxidation reactions of a conjugated bisallene.
Scheme 51: The mechanism of oxidation of the bisallene 24.
Scheme 52: CuCl-catalyzed cyclization of 1,2,4,5-hexatetraene (2).
Scheme 53: The conversion of conjugated bisallenes into cyclopentenones.
Scheme 54: Oligomerization of a conjugated bisallene by nickel catalysts.
Scheme 55: Generation of 1,2,5,6-heptatetraene (229) as a reaction intermediate.
Scheme 56: The preparation of a stable derivative of 1,2,5,6-heptatetraene.
Scheme 57: A bisallene with a carbonyl group as a spacer element.
Scheme 58: The first preparation of 1,2,6,7-octatetraene (242).
Scheme 59: Preparation of 1,2,6,7-octatetraenes by (C4 + C4)-coupling of enynes.
Scheme 60: Preparation of 1,2,6,7-octatetraenes by (C4 + C4)-coupling of homoallenyl bromides.
Scheme 61: Preparation of 1,2,6,7-octatetraenes by alkylation of propargylic substrates.
Scheme 62: Preparation of two highly functionalized 1,2,6,7-octatetraenes.
Scheme 63: Preparation of several higher α,ω-bisallenes.
Scheme 64: Preparation of different alkyl derivatives of α,ω-bisallenes.
Scheme 65: The preparation of functionalized 1,2,7,8-nonatetraene derivatives.
Scheme 66: Preparation of functionalized α,ω-bisallenes.
Scheme 67: The preparation of an α,ω-bisallene by direct homologation of an α,ω-bisalkyne.
Scheme 68: The gas-phase pyrolysis of 4,4-dimethyl-1,2,5,6-heptatetraene (237).
Scheme 69: Gas-phase pyrolysis of 1,2,6,7-octatetraene (242).
Scheme 70: The cyclopropanation of 1,2,6,7-octatetraene (242).
Scheme 71: Intramolecular cyclization of 1,2,6,7-octatetraene derivatives.
Scheme 72: The gas-phase pyrolysis of 1,2,7,8-nonatetraene (265) and 1,2,8,9-decatetraene (266).
Scheme 73: Rh-catalyzed cyclization of a functionalized 1,2,7,8-nonatetraene.
Scheme 74: A triple cyclization involving two different allenic substrates.
Scheme 75: Bicyclization of keto derivatives of 1,2,7,8-nonatetraene.
Scheme 76: The preparation of complex organic compounds from functionalized bisallenes.
Scheme 77: Cycloisomerization of an α,ω-bisallene containing a C9 tether.
Scheme 78: Organoborane polymers from α,ω-bisallenes.
Scheme 79: Preparation of trans- (337) and cis-1,2,4,6,7-octapentaene (341).
Scheme 80: The preparation of 4-methylene-1,2,5,6-heptatetraene (349).
Scheme 81: The preparation of acetylenic bisallenes.
Scheme 82: The preparation of derivatives of hydrocarbon 351.
Scheme 83: The construction of macrocyclic alleno-acetylenes.
Scheme 84: Preparation and reactions of 4,5-bismethylene-1,2,6,7-octatetraene (365).
Scheme 85: Preparation of 1,2-bis(propadienyl)benzene (370).
Scheme 86: The preparation of 1,4-bis(propadienyl)benzene (376).
Scheme 87: The preparation of aromatic and heteroaromatic bisallenes by metal-mediated coupling reactions.
Scheme 88: Double cyclization of an aromatic bisallene.
Scheme 89: Preparation of an allenic [15]paracyclophane by a ring-closing metathesis reaction of an aromatic α...
Scheme 90: Preparation of a macrocyclic ring system containing 1,4-bis(propadienyl)benzene units.
Scheme 91: Preparation of copolymers from 1,4-bis(propadienyl)benzene (376).
Scheme 92: A boration/copolymerization sequence of an aromatic bisallene and an aromatic bisacetylene.
Scheme 93: Formation of a layered aromatic bisallene.
Figure 4: The first members of the semicyclic bisallene series.
Scheme 94: Preparation of the first bis(vinylidene)cyclobutane derivative.
Scheme 95: Dimerization of strain-activated cumulenes to bis(vinylidene)cyclobutanes.
Scheme 96: Photodimerization of two fully substituted butatrienes in the solid state.
Scheme 97: Preparation of the two parent bis(vinylidene)cyclobutanes.
Scheme 98: The preparation of 1,3-bis(vinylidene)cyclopentane and its thermal isomerization.
Scheme 99: The preparation of the isomeric bis(vinylidene)cyclohexanes.
Scheme 100: Bi- and tricyclic conjugated bisallenes.
Scheme 101: A selection of polycyclic bisallenes.
Scheme 102: The first endocyclic bisallenes.
Figure 5: The stereochemistry of 1,2,6,7-cyclodecatetraene.
Scheme 103: The preparation of several endocyclic bisallenes.
Scheme 104: Synthesis of diastereomeric derivatives of 1,2,6,7-cyclodecatetraene.
Scheme 105: Preparation of a derivative of 1,2,8,9-cyclotetradecatetraene.
Scheme 106: The preparation of keto derivatives of cyclic bisallenes.
Scheme 107: The preparation of cyclic biscumulenic ring systems.
Scheme 108: Cyclic bisallenes in natural- and non-natural-product chemistry.
Scheme 109: The preparation of iron carbonyl complexes from cyclic bisallenes.
Figure 6: A selection of unknown exocyclic bisallenes that should have interesting chemical properties.
Scheme 110: The thermal isomerization of 1,2-diethynylcyclopropanes and -cyclobutanes.
Scheme 111: Intermediate generation of a cyclooctapentaene.
Scheme 112: Attempted preparation of a cyclodecahexaene.
Scheme 113: The thermal isomerization of 1,5,9-cyclododecatriyne (511) into [6]radialene (514).
Scheme 114: An isomerization involving a diketone derived from a conjugated bisallene.
Scheme 115: Typical reaction modes of heteroorganic bisallenes.
Scheme 116: Generation and thermal behavior of acyclic hetero-organic bisallenes.
Scheme 117: Generation of bis(propadienyl)thioether.
Scheme 118: The preparation of a bisallenic sulfone and its thermal isomerization.
Scheme 119: Bromination of the bisallenic sulfone 535.
Scheme 120: Metalation/hydrolysis of the bisallenic sulfone 535.
Scheme 121: Aromatic compounds from hetero bisallenes.
Scheme 122: Isomerization/cyclization of bispropargylic ethers.
Scheme 123: The preparation of novel aromatic systems by base-catalyzed isomerization of bispropargyl ethers.
Scheme 124: The isomerization of bisacetylenic thioethers to bicyclic thiophenes.
Scheme 125: Aromatization of macrocyclic bispropargylic sulfides.
Scheme 126: Preparation of ansa-compounds from macrocyclic bispropargyl thioethers.
Scheme 127: Alternate route for cyclization of a heterorganic bisallene.
Scheme 128: Multiple isomerization/cyclization of “double” bispropargylic thioethers.
Scheme 129: Preparation of a bisallenyl disulfide and its subsequent bicyclization.
Scheme 130: Thermal cyclization of a bisallenyl thiosulfonate.
Scheme 131: Some reactions of heteroorganic bisallenes with two sulfur atoms.
Scheme 132: Further methods for the preparation of heteroorganic bisallenes.
Scheme 133: Cyclization reactions of heteroorganic bisallenes.
Scheme 134: Thermal cycloadditions of bisallenic tertiary amines.
Scheme 135: Cyclization of a bisallenic tertiary amine in the presence of a transition-metal catalyst.
Scheme 136: A Pauson–Khand reaction of a bisallenic ether.
Scheme 137: Formation of a 2:1adduct from two allenic substrates.
Scheme 138: A ring-forming silastannylation of a bisallenic tertiary amine.
Scheme 139: A three-component cyclization involving a heterorganic bisallene.
Scheme 140: Atom-economic construction of a complex organic framework from a heterorganic α,ω-bisallene.
Molecular solubilization of fullerene C60 in water by γ-cyclodextrin thioethers
- Hai Ming Wang and
- Gerhard Wenz
Beilstein J. Org. Chem. 2012, 8, 1644–1651, doi:10.3762/bjoc.8.188
- much lower aggregation tendency than the corresponding ones of native γ-CD. Molecular solubilization of fullerene C60 in water, reaching concentrations as high as 15 μM, was achieved in the presence of 6.0 mM of a γ-CD thioether. The resulting aqueous molecular solutions of C60 free of toxic organic
- solvents will hopefully find interesting applications in biomedicine, such as in photodynamic therapy or HIV-protease inhibition. Experimental General Unless otherwise stated, all chemicals were used as received. Powdered fullerene C60 (> 99%) was purchased from Sigma Aldrich. Teflon syringe filters from
Graphical Abstract
Figure 1: Space-filling model of the most stable complex between γ-CD and C60 with 1:2 stoichiometry, calcula...
Scheme 1: Chemical structures of γ-CD and γ-CD thioether 1–7 used to solubilize C60 in water.
Figure 2: UV–vis spectra of (a) C60 solution in THF, (b) aqueous solutions of C60 with 6 mM γ-CD thioether 5 ...
Figure 3: Isothermal kinetics of the dissolution of C60 in the presence of 10 mM CD 7 in water. Curve: best f...
Scheme 2: Mechanistic description of the two possible mechanisms for the complexation of C60 (G) by CD hosts,...
Figure 4: Phase-solubility diagram of C60 in aqueous solution in the presence of CD 3.
Figure 5: UV–vis spectra of the water solution of C60 produced by stirring C60 in 6mM γ-CD solution in DMF/to...
Figure 6: Size distribution of the molecular solution of C60 with 6 mM CD 5 in water at 25.0 °C: before centr...
Figure 7: Size distributions of the aqueous C60 dispersions after filtration, produced by stirring C60 in 6mM...
Control over molecular motion using the cis–trans photoisomerization of the azo group
- Estíbaliz Merino and
- María Ribagorda
Beilstein J. Org. Chem. 2012, 8, 1071–1090, doi:10.3762/bjoc.8.119
- : A central azobenzene, a rigid frame composed of oligo(phenylacetylenes), which in turn are anchored to azobenzene through para positions, and wheels based on fullerene C60 (azo-14) or p-carboranes (azo-15). Photoisomerization studies suggest that only the azobenzene system with p-carborane wheels
- (azo-15) may be useful as a molecular switch, because the photoisomerization of azo-fullerene 14 leads to only 8% of the cis-isomer. Although, the quantum yield obtained for cis-14 is not very high, this proportion is significant, given the speed with which energy transfer to the fullerene unit occurs
Graphical Abstract
Figure 1: Photoisomerization process of azobenzene.
Figure 2: Representative example of an UV spectrum of an azocompound of the azobenzene type (blue line: trans...
Figure 3: Mechanistic proposals for the isomerization of azobenzenes.
Figure 4: Representation of the photocontrol of a K+ channel in the cellular membrane based on the isomerizat...
Figure 5: (a) MAG interaction with iGluR; (b) photocontrol of the opening of the ion channel by trans–cis iso...
Figure 6: Photocontrol of the structure of the α-helix in the polypeptide azoderivative 2. Reprinted (adapted...
Figure 7: Recognition of a guanidinium ion by a cis,cis-bis-azo derivative 3.
Figure 8: Recognition of cesium ions by cis-azo derivative 4.
Figure 9: Photocontrolled formation of an inclusion complex of cyclodextrin trans-azo 5+6.
Figure 10: Pseudorotaxane-based molecular machine.
Figure 11: Molecular hinge. Reprinted (adapted) with permission from Org. Lett. 2004, 6, 2595–2598. Copyright ...
Figure 12: Molecular threader. Reprinted (adapted) with permission from Acc. Chem. Res. 2001, 34, 445–455. Cop...
Figure 13: Molecular scissors based on azobenzene 12. Reprinted (adapted) with permission from J. Am. Chem. So...
Figure 14: Molecular pedals. Reprinted by permission from Macmillan Publishers Ltd: Nature, 2006, 440, 512–515...
Figure 15: Design of nanovehicles based on azo structures. Reprinted (adapted) with permission from Org. Lett. ...
Figure 16: Light-activated mesostructured silica nanoparticles (LAMs).
Figure 17: Molecular lift.
Figure 18: Conformational considerations in mono-ortho-substituted azobenzenes.
Scheme 1: Synthesis and photoisomerization of sulfinyl azobenzenes. Reprinted (adapted) with permission from ...
Figure 19: Photoisomerization of azocompound 22 and its application as a photobase catalyst.
Figure 20: Effect of irradiation with linearly polarized light on azo-LCEs. Reprinted by permission from Macmi...
Figure 21: Chemically and photochemically triggered memory switching cycle of the [2]rotaxane 25.
Figure 22: Unidirectional photoisomerization process of the azobenzene 26.
Low-generation dendrimers with a calixarene core and based on a chiral C2-symmetric pyrrolidine as iminosugar mimics
- Marco Marradi,
- Stefano Cicchi,
- Francesco Sansone,
- Alessandro Casnati and
- Andrea Goti
Beilstein J. Org. Chem. 2012, 8, 951–957, doi:10.3762/bjoc.8.107
- interactions [10], the effect of iminosugar-based multivalent inhibitors on enzyme activity is difficult to rationalise. However, the introduction of several copies of an N-alkyl analogue of iminosugar 1-deoxynojirimycin onto a fullerene ball [8] or onto β-cyclodextrin [9] afforded the first pieces of evidence
Graphical Abstract
Figure 1: First (2) and second (3) generation of dendrimers based on chiral C2-symmetric pyrrolidine 1 and ha...
Scheme 1: Use of the key intermediate (3S,4S)-1-benzyl-3,4-dihydroxypyrrolidine (6) [31] for the synthesis of pyr...
Scheme 2: Synthesis of calixarene-based dendrimers 2 and 3. Reagents and conditions: DIPEA, CH2Cl2, 30 °C, 5 ...
Figure 2: Expansion (about 7 to 3 ppm) of the 1H NMR spectra of (A) the free ligand 2, (B) the sodium picrate...
Figure 3: Schematic of the inclusion of alkali-metal ions (sodium and potassium) in the polar cavity defined ...
Synthesis and mesomorphic properties of calamitic malonates and cyanoacetates tethered to 4-cyanobiphenyls
- Katharina C. Kress,
- Martin Kaller,
- Kirill V. Axenov,
- Stefan Tussetschläger and
- Sabine Laschat
Beilstein J. Org. Chem. 2012, 8, 371–378, doi:10.3762/bjoc.8.40
- malonates has been devoted to C60 fullerene dendrimers [27][28][29][30][31]. Only a few liquid crystalline cyanoacetates have been described so far. The first example, a dihydrazide, was reported by Schubert [32]. Furthermore some calamitic and bent-core mesogens derived from α-cyanocinnamic acid were
Graphical Abstract
Scheme 1: Diketonato metallomesogens and diketones with mesomorphic properties.
Scheme 2: Malonates and cyanoacetates tethered to calamitic 4-cyanobiphenyl units.
Scheme 3: Synthesis of malonate and cyanoacetates tethered to 4-cyano-biphenyl moieties.
Figure 1: DSC traces of 13a (heating/cooling rate 5 K/min).
Figure 2: DSC traces of 11a (heating/cooling rate 10 K/min).
Figure 3: Schlieren textures of 11a and 11b under crossed polarizers, upon cooling (cooling rate 5 K/min) fro...
Figure 4: Schlieren textures of 13a and 13b under crossed polarizers upon cooling (cooling rate 5 K/min) from...
Figure 5: 2D X-ray scattering patterns of 11a: (A) crystalline phase at 50 °C, (B) isotropic phase at 25 °C, ...
Fifty years of oxacalix[3]arenes: A review
- Kevin Cottet,
- Paula M. Marcos and
- Peter J. Cragg
Beilstein J. Org. Chem. 2012, 8, 201–226, doi:10.3762/bjoc.8.22
- species. Applications in fields as diverse as ion selective electrode modifiers, fluorescence sensors, fullerene separations and biomimetic chemistry are described. Keywords: calixarenes; host–guest chemistry; macrocycles; oxacalixarenes; Introduction Calixarenes, macrocycles which are widely used in
- subtle spectroscopic features and computer models appeared to indicate fullerene binding, structural evidence was to be more compelling. In 1998, Fuji reported the solid-state structure of 3f with C60 as proof of 1:1 binding [76]. Alignment of the oxacalix[3]arene C3 axis with the same symmetry axis of
- to a combination of several factors, of which host–C60 complex formation is only one [77]. Consequently, reported Kassoc values determined by this method should be treated with some caution. Fullerene derivatives that lack some of the symmetry of the parent compound have been shown to bind to
Graphical Abstract
Figure 1: Calixarenes and expanded calixarenes: p-tert-Butylcalix[4]arene (1), p-tert-butyldihomooxacalix[4]a...
Figure 2: Conventional nomenclature for oxacalix[n]arenes.
Scheme 1: Synthesis of oxacalix[3]arenes: (i) Formaldehyde (37% aq), NaOH (aq), 1,4-dioxane; glacial acetic a...
Figure 3: p-tert-Butyloctahomotetraoxacalix[4]arene (4a) [16].
Figure 4: X-ray crystal structure of 3a showing phenolic hydrogen bonding (IUCr ID AS0508) [17].
Scheme 2: Stepwise synthesis of asymmetric oxacalix[3]arenes: (i) MOMCl, Adogen®464; (ii) 2,2-dimethoxypropan...
Figure 5: X-ray crystal structure of heptahomotetraoxacalix[3]arene 5 (CCDC ID 166088) [21].
Scheme 3: Oxacalix[3]arene synthesis by reductive coupling: (i) Me3SiOTf, Et3SiH, CH2Cl2; R1, R2 = I, Br, ben...
Scheme 4: Oxacalix[3]naphthalene: (i) HClO4 (aq), wet CHCl3 (R = tert-butyl, 6a, H, 6b) [20].
Figure 6: Conformers of 3a.
Scheme 5: Origin of the 25:75 cone:partial-cone statistical distribution of O-substituted oxacalix[3]arenes (p...
Scheme 6: Synthesis of alkyl ethers 7–10: (i) Alkyl halide, NaH, DMF [24].
Scheme 7: Synthesis of a pyridyl derivative 11a: (i) Picolyl chloride hydrochloride, NaH, DMF [26,27].
Figure 7: X-ray crystal structure of partial-cone 11a (CCDC ID 150580) [26].
Scheme 8: Lower-rim ethyl ester synthesis: (i) Ethyl bromoacetate, NaH, t-BuOK or alkali metal carbonate, THF...
Scheme 9: Forming chiral receptor 13: (i) Ethyl bromoacetate, NaH, THF; (ii) NaOH, H2O/1,4-dioxane; (iii) S-P...
Figure 8: X-ray crystal structure of 16 (IUCr ID PA1110) [32].
Scheme 10: Lower rim N,N-diethylamide 17a: (i) N,N-Diethylchloroacetamide, NaH, t-BuOK or alkali metal carbona...
Scheme 11: Capping the lower rim: (i) N,N-Diethylchloroacetamide, NaH, THF; (ii) NaOH, H2O/1,4-dioxane; (iii) ...
Figure 9: X-ray crystal structure of 18 (CCDC ID 142599) [33].
Scheme 12: Extending the lower rim: (i) Glycine methyl ester, HOBt, dicyclohexycarbodiimide (DCC), CH2Cl2; (ii...
Scheme 13: Synthesis of N-hydroxypyrazinone derivative 23: (i) 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide...
Scheme 14: Synthesis of 24: (i) 1-Adamantyl bromomethyl ketone, NaH, THF [39].
Scheme 15: Synthesis of 25 and 26: (i) (Diphenylphosphino)methyl tosylate, NaH, toluene; (ii) phenylsilane, to...
Figure 10: X-ray crystal structure of 27 in the partial-cone conformer (CCDC ID SUP 90399) [41].
Scheme 16: Synthesis of strapped oxacalix[3]arene derivatives 28 and 29: (i) N,N’-Bis(chloroacetyl)-1,2-ethyle...
Figure 11: A chiral oxacalix[3]arene [45].
Figure 12: X-ray crystal structure of asymmetric oxacalix[3]arene 30 incorporating t-Bu, iPr and Et groups (CC...
Scheme 17: Reactions of an oxacalix[3]arene incorporating an upper-rim Br atom with (i) Pd(OAc)2, PPh3, HCO2H,...
Scheme 18: Synthesis of acid 39: (i) NaOH, EtOH/H2O, HCl (aq) [47].
Figure 13: Two forms of dimeric oxacalix[3]arene 40 [47].
Scheme 19: Capping the upper rim: (i) t-BuLi, THF, −78 °C; (ii) NaBH4, THF/EtOH; (iii) 1,3,5-tris(bromomethyl)...
Figure 14: Oxacalix[3]arene capsules 46 and 47 formed through coordination chemistry [52,53].
Figure 15: X-ray crystal structure of the 3b-vanadyl complex (CCDC ID 240185) [57].
Scheme 20: Effect of Ti(IV)/SiO2 on 3a: (i) Ti(OiPr)4, toluene; (ii) triphenylsilanol, toluene; (iii) partiall...
Figure 16: X-ray crystal structures of oxacalix[3]arene complexes with rhenium: 3b∙Re(CO)3 (CCDC ID 620981, le...
Figure 17: X-ray crystal structure of the La2·3a2 complex (CSD ID TIXXUT) [60].
Figure 18: X-ray crystal structures of [3a∙UO2]− with a cavity-bound cation (CCDC ID 135575, left) and without...
Figure 19: X-ray crystal structure of a supramolecule comprising two [3g·UO2]− complexes that encapsulate a di...
Figure 20: X-ray crystal structure of oxacalix[3]arene 49 capable of chiral selectivity (CSD ID HIGMUF) [65].
Figure 21: The structure of derivative 50 incorporating a Reichardt dye [66].
Figure 22: Phosphorylated oxacalix[3]arene complexes with transition metals: (Left to right) 26∙Au, 26∙Mo(CO)3...
Figure 23: X-ray crystal structure of [17a·HgCl2]2 (CCDC ID 168653) [69].
Figure 24: X-ray crystal structures of 3f with C60 (CCDC ID 182801, left) [76] and a 1,4-bis(9-fluorenyl) C60 deri...
Figure 25: X-Ray crystal structure of 3i and 6a encapsulating C60 (CCDC ID 102473 and 166077) [23,79].
Figure 26: A C60 complexing cationic oxacalix[3]arene 51 [81].
Figure 27: An oxacalix[3]arene-C60 self-associating system 53 [87].
Scheme 21: Synthesis of fluorescent pyrene derivative 55: (i) Propargyl bromide, acetone; (ii) CuI, 1-azidomet...
Scheme 22: Synthesis of responsive rhodamine derivative 57: (i) DCC, CH2Cl2 [91].
Scheme 23: Synthesis of nitrobenzyl derivative 58: (i) 1-Bromo-4-nitrobenzyl acetate, K2CO3, refluxing acetone...
Figure 28: X-ray crystal structure of [Na2∙17a](PF6)2 (CCDC ID 116656) [97].
Imidazole as a parent π-conjugated backbone in charge-transfer chromophores
- Jiří Kulhánek and
- Filip Bureš
Beilstein J. Org. Chem. 2012, 8, 25–49, doi:10.3762/bjoc.8.4
- effort resulted in organic photovoltaic devices with a very high fill factor FF = 57% and an external quantum efficiency IPCE (incident photons converted to electrons) = 27%. These values rival those measured for popular fullerene acceptors. Imidazole chromophores incorporated into the polymer Recently
Graphical Abstract
Figure 1: Schematic representation of organic D-π-A system featuring ICT.
Figure 2: Two principal orientations of the imidazole-derived charge-transfer chromophores.
Scheme 1: Common synthetic approach to triarylimidazole-, diimidazole-, and benzimidazole-derived CT chromoph...
Scheme 2: Syntheses of important 4,5-dicyanoimidazole derivatives 1–3 [27-30].
Figure 3: Donor–acceptor triaryl push–pull azoles 4a–h [31,32].
Figure 4: Y-shaped CT chromophores with an extended π-conjugated pathway and various donor and acceptor subst...
Figure 5: Molecular structures of chromophores 9–14 [13,15,37-41].
Figure 6: General structure of 4,5-bis(4-aminophenyl)imidazole-derived chromophores 15a–g with various π-link...
Figure 7: Various orientations of the substituents on the parent lophine π-conjugated backbone (16–19) and th...
Figure 8: Structure and electronic absorption spectra of chromophores 21–26 [12].
Figure 9: Typical D-π-A diimidazole CT chromophore [16-18,50-53].
Figure 10: Typical D-π-D diimidazoles 28–31 [19,54-56] and photochromic diimidazoles 32,33 [57,58].
Scheme 3: Oxidation of 1H-diimidazoles to 2H-diimidazoles (quinoids).
Figure 11: Typical benzimidazoles-derived D-π-A push–pull systems 35–43 [25,62-66].
Figure 12: Structure of benzimidazoles (44–47), imidazophenanthrolines (48–57), imidazophenanthrenes (58–60), ...
Scheme 4: Acidoswitchable NLO-phores 64,65 and ESIPT mechanism [72-74].
Figure 13: General structures of bis(benzimidazole) chromophores 67–71 and pyridinium betaines 72 [75-79].
Figure 14: Overview of 4,5-dicyanoimidazole derivatives investigated by Rasmussen et al. [29,81-94].
Figure 15: 4,5-Dicyanoimidazole-derived chromophores 84–87 [103-106].
Figure 16: Push–pull chromophores 88–93 with systematically extended π-linker [30].
Figure 17: pH-triggered NLO switches 88c–93c [109].
Figure 18: Dibromoolefin 94 and branched chromophores 95–100 [112,113].
Figure 19: Imidazole as a donor–acceptor unit in CT-chromophores 101–111 [20].
Figure 20: Diimidazoles 112–115 used as small electron acceptors in organic solar cells [115,116].
Figure 21: Amino- and hydroxy-functionalized chromophores incorporated into a polymer backbone Rpol [18,50-53,122-124].
Figure 22: Structure of polyphosphazene polymers bearing NLO-phores [125-127] and some other recent examples of nonline...
Figure 23: Epoxy- and silica-based polymers functionalized with 4,5-dicyanoimidazole unit [105,130].
Self-assembly and semiconductivity of an oligothiophene supergelator
- Pampa Pratihar,
- Suhrit Ghosh,
- Vladimir Stepanenko,
- Sameer Patwardhan,
- Ferdinand C. Grozema,
- Laurens D. A. Siebbeles and
- Frank Würthner
Beilstein J. Org. Chem. 2010, 6, 1070–1078, doi:10.3762/bjoc.6.122
- concentration of 5 x 10−5 M. Studies on blends of T1 with PCBM The fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is a well-known n-type semiconductor and its blends with various electron-donor materials have been extensively used in solar cell devices [24]. The morphology of the blend
Graphical Abstract
Scheme 1: Structure of the quarterthiophene derivative T1.
Scheme 2: Synthetic route to T1. Reagent and conditions: a) Boc anhydride, CH2Cl2, 6 h, 0 °C–rt, 97%; b) NBS,...
Figure 1: AFM height images of a film spin-coated from diluted gel solution of T1 in MCH (2 × 10−3 M) onto HO...
Figure 2: a) UV-vis spectra of T1 in chloroform (dashed line) and n-heptane (solid line); b) UV-vis spectra o...
Scheme 3: Proposed mode of self-assembly of T1.
Figure 3: UV-vis spectra of T1 (concentration 5 x 10−5 M) in cyclohexane (solid line) and 2.4% MeOH in cycloh...
Figure 4: AFM height images (A and B) of a film spin-coated from MCH solution (concentration 5 x 10−4 M) of a...
Figure 5: Variation of dose-normalized conductivity transients (Δσ/D) with time for T1.
Molecular recognition of organic ammonium ions in solution using synthetic receptors
- Andreas Späth and
- Burkhard König
Beilstein J. Org. Chem. 2010, 6, No. 32, doi:10.3762/bjoc.6.32
Graphical Abstract
Figure 1: Biologically important amines and quaternary ammonium salts: histamine (1), dopamine (2) and acetyl...
Figure 2: Crown ether 18-crown-6.
Figure 3: Conformations of 18-crown-6 (4) in solvents of different polarity.
Figure 4: Binding topologies of the ammonium ion depending on the crown ring size.
Figure 5: A “pseudorotaxane” structure consisting of 24-crown-8 and a secondary ammonium ion (5); R = Ph.
Figure 6: Typical examples of azacrown ethers, cryptands and related aza macrocycles.
Figure 7: Binding of ammonium to azacrown ethers and cryptands [111-113].
Figure 8: A 19-crown-6-ether with decalino blocking groups (11) and a thiazole-dibenzo-18-crown-6-ether (12).
Figure 9: 1,3-Bis(6-oxopyridazin-1-yl)propane derivatives 13 and 14 by Campayo et al.
Figure 10: Fluorescent azacrown-PET-sensors based on coumarin.
Figure 11: Two different pyridino-cryptands (17 and 18) compared to a pyridino-crown (19); chiral ammonium ion...
Figure 12: Pyridino-18-crown-6 ligand (21), a similar acridino-18-crown-6 ligand (22) and a structurally relat...
Figure 13: Ciral pyridine-azacrown ether receptors 24.
Figure 14: Chiral 15-crown-5 receptors 26 and an analogue 18-crown-6 ligand 27 derived from amino alcohols.
Figure 15: C2-symmetric chiral 18-crown-6 amino alcohol derivatives 28 and related macrocycles.
Figure 16: Macrocycles with diamide-diester groups (30).
Figure 17: C2-symmetric chiral aza-18-crown-6 ethers (31) with phenethylamine residues.
Figure 18: Chiral C-pivot p-methoxy-phenoxy-lariat ethers.
Figure 19: Chiral lariat crown ether 34.
Figure 20: Sucrose-based chiral crown ether receptors 36.
Figure 21: Permethylated fructooligosaccharide 37 showing induced-fit chiral recognition.
Figure 22: Biphenanthryl-18-crown-6 derivative 38.
Figure 23: Chiral lariat crown ethers derived from binol by Fuji et al.
Figure 24: Chiral phenolic crown ether 41 with “aryl chiral barriers” and guest amines.
Figure 25: Chiral bis-crown receptor 43 with a meso-ternaphthalene backbone.
Figure 26: Chromogenic pH-dependent bis-crown chemosensor 44 for diamines.
Figure 27: Triamine guests for binding to receptor 44.
Figure 28: Chiral bis-crown phenolphthalein chemosensors 46.
Figure 29: Crown ether amino acid 47.
Figure 30: Luminescent receptor 48 for bis-alkylammonium guests.
Figure 31: Luminescent CEAA (49a), a bis-CEAA receptor for amino acids (49b) and the structure of lysine bindi...
Figure 32: Luminescent CEAA tripeptide for binding small peptides.
Figure 33: Bis crown ether 51a self assembles co-operatively with C60-ammonium ion 51b.
Figure 34: Triptycene-based macrotricyclic dibenzo-[24]-crown-8 ether host 52 and guests.
Figure 35: Copper imido diacetic acid azacrown receptor 53a and the suggested His-Lys binding motif; a copper ...
Figure 36: Urea (54) and thiourea (55) benzo crown receptor for transport and extraction of amino acids.
Figure 37: Crown pyryliums ion receptors 56 for amino acids.
Figure 38: Ditopic sulfonamide bridged crown ether receptor 57.
Figure 39: Luminescent peptide receptor 58.
Figure 40: Luminescent receptor 59 for the detection of D-glucosamine hydrochloride in water/ethanol and lumin...
Figure 41: Guanidinium azacrown receptor 61 for simple amino acids and ditopic receptor 62 with crown ether an...
Figure 42: Chiral bicyclic guanidinium azacrown receptor 63 and similar receptor 64 for the enantioselective t...
Figure 43: Receptors for zwitterionic species based on luminescent CEAAs.
Figure 44: 1,10-Azacrown ethers with sugar podand arms and the anticancer agent busulfan.
Figure 45: Benzo-18-crown-6 modified β-cyclodextrin 69 and β-cyclodextrin functionalized with diaza-18-crown-6...
Figure 46: Receptors for colorimetric detection of primary and secondary ammonium ions.
Figure 47: Porphyrine-crown-receptors 72.
Figure 48: Porphyrin-crown ether conjugate 73 and fullerene-ammonium ion guest 74.
Figure 49: Calix[4]arene (75a), homooxocalix[4]arene (75b) and resorcin[4]arene (75c) compared (R = H, alkyl c...
Figure 50: Calix[4]arene and ammonium ion guest (R = H, alkyl, OAcyl etc.), possible binding sites; A: co-ordi...
Figure 51: Typical guests for studies with calixarenes and related molecules.
Figure 52: Lower rim modified p-tert-butylcalix[5]arenes 82.
Figure 53: The first example of a water soluble calixarene.
Figure 54: Sulfonated water soluble calix[n]arenes that bind ammonium ions.
Figure 55: Displacement assay for acetylcholine (3) with a sulfonato-calix[6]arene (84b).
Figure 56: Amino acid inclusion in p-sulfonatocalix[4]arene (84a).
Figure 57: Calixarene receptor family 86 with upper and lower rim functionalization.
Figure 58: Calix[6]arenes 87 with one carboxylic acid functionality.
Figure 59: Sulfonated calix[n]arenes with mono-substitution at the lower rim systematically studied on their r...
Figure 60: Cyclotetrachromotropylene host (91) and its binding to lysine (81c).
Figure 61: Calixarenes 92 and 93 with phosphonic acids groups.
Figure 62: Calix[4]arene tetraphosphonic acid (94a) and a double bridged analogue (94b).
Figure 63: Calix[4]arene tetraphosphonic acid ester (92c) for surface recognition experiments.
Figure 64: Calixarene receptors 95 with α-aminophosphonate groups.
Figure 65: A bridged homocalix[3]arene 95 and a distally bridged homocalix[4]crown 96.
Figure 66: Homocalix[3]arene ammonium ion receptor 97a and the Reichardt’s dye (97b) for colorimetric assays.
Figure 67: Chromogenic diazo-bridged calix[4]arene 98.
Figure 68: Calixarene receptor 99 by Huang et al.
Figure 69: Calixarenes 100 reported by Parisi et al.
Figure 70: Guest molecules for inclusion in calixarenes 100: DAP × 2 HCl (101a), APA (101b) and Lys-OMe × 2 HC...
Figure 71: Different N-linked peptido-calixarenes open and with glycol chain bridges.
Figure 72: (S)-1,1′-Bi-2-naphthol calixarene derivative 104 published by Kubo et al.
Figure 73: A chiral ammonium-ion receptor 105 based on the calix[4]arene skeleton.
Figure 74: R-/S-phenylalaninol functionalized calix[6]arenes 106a and 106b.
Figure 75: Capped homocalix[3]arene ammonium ion receptor 107.
Figure 76: Two C3 symmetric capped calix[6]arenes 108 and 109.
Figure 77: Phosphorous-containing rigidified calix[6]arene 110.
Figure 78: Calix[6]azacryptand 111.
Figure 79: Further substituted calix[6]azacryptands 112.
Figure 80: Resorcin[4]arene (75c) and the cavitands (113).
Figure 81: Tetrasulfonatomethylcalix[4]resorcinarene (114).
Figure 82: Resorcin[4]arenes (115a/b) and pyrogallo[4]arenes (115c, 116).
Figure 83: Displacement assay for acetylcholine (3) with tetracyanoresorcin[4]arene (117).
Figure 84: Tetramethoxy resorcinarene mono-crown-5 (118).
Figure 85: Components of a resorcinarene based displacement assay for ammonium ions.
Figure 86: Chiral basket resorcin[4]arenas 121.
Figure 87: Resorcinarenes with deeper cavitand structure (122).
Figure 88: Resorcinarene with partially open deeper cavitand structure (123).
Figure 89: Water-stabilized deep cavitands with partially structure (124, 125).
Figure 90: Charged cavitands 126 for tetralkylammonium ions.
Figure 91: Ditopic calix[4]arene receptor 127 capped with glycol chains.
Figure 92: A calix[5]arene dimer for diammonium salt recognition.
Figure 93: Calixarene parts 92c and 129 for the formation molecular capsules.
Figure 94: Encapsulation of a quaternary ammonium cation by two resorcin[4]arene molecules (NMe4+@[75c]2 × Cl−...
Figure 95: Encapsulation of a quaternary ammonium cation by six resorcin[4]arene molecules (NMe3D+@[130]6 × Cl−...
Figure 96: Structure and schematic of cucurbit[6]uril (CB[6], 131a).
Figure 97: Cyclohexanocucurbit[6]uril (CB′[6], 132) and the guest molecule spermine (133).
Figure 98: α,α,δ,δ-Tetramethylcucurbit[6]uril (134).
Figure 99: Structure of the cucurbituril-phthalhydrazide analogue 135.
Figure 100: Organic cavities for the displacement assay for amine differentiation.
Figure 101: Displacement assay methodology for diammonium- and related guests involving cucurbiturils and some ...
Figure 102: Nor-seco-Cucurbituril (±)-bis-ns-CB[6] (140) and guest molecules.
Figure 103: The cucurbit[6]uril based complexes 141 for chiral discrimination.
Figure 104: Cucurbit[7]uril (131c) and its ferrocene guests (142) opposed.
Figure 105: Cucurbit[7]uril (131c) guest inclusion and representative guests.
Figure 106: Cucurbit[7]uril (131c) binding to succinylcholine (145) and different bis-ammonium and bis-phosphon...
Figure 107: Paraquat-cucurbit[8]uril complex 149.
Figure 108: Gluconuril-based ammonium receptors 150.
Figure 109: Examples of clefts (151a), tweezers (151b, 151c, 151d) and clips (151e).
Figure 110: Kemp’s triacid (152a), on example of Rebek’s receptors (152b) and guests.
Figure 111: Amino acid receptor (154) by Rebek et al.
Figure 112: Hexagonal lattice designed hosts by Bell et al.
Figure 113: Bell’s amidinium receptor (156) and the amidinium ion (157).
Figure 114: Aromatic phosphonic acids.
Figure 115: Xylene phosphonates 159 and 160a/b for recognition of amines and amino alcohols.
Figure 116: Bisphosphonate recognition motif 161 for a colorimetric assay with alizarin complexone (163) for ca...
Figure 117: Bisphosphonate/phosphate clip 164 and bisphosphonate cleft 165.
Figure 118: N-Methylpyrazine 166a, N-methylnicotinamide iodide (166b) and NAD+ (166c).
Figure 119: Bisphosphate cavitands.
Figure 120: Bisphosphonate 167 of Schrader and Finocchiaro.
Figure 121: Tweezer 168 for noradrenaline (80b).
Figure 122: Different tripods and heparin (170).
Figure 123: Squaramide based receptors 172.
Figure 124: Cage like NH4+ receptor 173 of Kim et al.
Figure 125: Ammonium receptors 174 of Chin et al.
Figure 126: 2-Oxazolin-based ammonium receptors 175a–d and 176 by Ahn et al.
Figure 127: Racemic guest molecules 177.
Figure 128: Tripods based on a imidazole containing macrocycle (178) and the guest molecules employed in the st...
Figure 129: Ammonium ion receptor 180.
Figure 130: Tetraoxa[3.3.3.3]paracyclophanes 181 and a cyclophanic tetraester (182).
Figure 131: Peptidic bridged paraquat-cyclophane.
Figure 132: Shape-selective noradrenaline host.
Figure 133: Receptor 185 for binding of noradrenaline on surface layers from Schrader et al.
Figure 134: Tetraphosphonate receptor for binding of noradrenaline.
Figure 135: Tetraphosphonate 187 of Schrader and Finocchiaro.
Figure 136: Zinc-Porphyrin ammonium-ion receptors 188 and 189 of Mizutani et al.
Figure 137: Zinc porphyrin receptor 190.
Figure 138: Zinc porphyrin receptors 191 capable of amino acid binding.
Figure 139: Zinc-porphyrins with amino acid side chains for stereoinduction.
Figure 140: Bis-zinc-bis-porphyrin based on Tröger’s base 193.
Figure 141: BINAP-zinc-prophyrin derivative 194 and it’s guests.
Figure 142: Bisaryl-linked-zinc-porphyrin receptors.
Figure 143: Bis-zinc-porphyrin 199 for diamine recognition and guests.
Figure 144: Bis-zinc-porphyrin crown ether 201.
Figure 145: Bis-zinc-porphyrin 202 for stereodiscrimination (L = large substituent; S = small substituent).
Figure 146: Bis-zinc-porphyrin[3]rotaxane and its copper complex and guests.
Figure 147: Dien-bipyridyl ligand 206 for co-ordination of two metal atoms.
Figure 148: The ligand and corresponding tetradentate co-complex 207 serving as enantioselective receptor for a...
Figure 149: Bis(oxazoline)–copper(II) complex 208 for the recognition of amino acids in aqueous solution.
Figure 150: Zinc-salen-complexes 209 for the recognition tertiary amines.
Figure 151: Bis(oxazoline)–copper(II) 211 for the recognition of amino acids in aqueous solution.
Figure 152: Zn(II)-complex of a C2 terpyridine crown ether.
Figure 153: Displacement assay and receptor for aspartate over glutamate.
Figure 154: Chiral complex 214 for a colorimetric displacement assay for amino acids.
Figure 155: Metal complex receptor 215 with tripeptide side arms.
Figure 156: A sandwich complex 216 and its displaceable dye 217.
Figure 157: Lanthanide complexes 218–220 for amino acid recognition.
Figure 158: Nonactin (221), valinomycin (222) and vancomycin (223).
Figure 159: Monesin (224a) and a chiral analogue for enantiodiscrimination of ammonium guests (224b).
Figure 160: Chiral podands (226) compared to pentaglyme-dimethylether (225) and 18-crown-6 (4).
Figure 161: Lasalocid A (228).
Figure 162: Lasalocid derivatives (230) of Sessler et al.
Figure 163: The Coporphyrin I tetraanion (231).
Figure 164: Linear and cyclic peptides for ammonium ion recognition.
Figure 165: Cyclic and bicyclic depsipeptides for ammonium ion recognition.
Figure 166: α-Cyclodextrin (136a) and novocaine (236).
Figure 167: Helical diol receptor 237 by Reetz and Sostmann.
Figure 168: Ammonium binding spherand by Cram et al. (238a) and the cyclic[6]metaphenylacetylene 238b in compar...
Figure 169: Receptor for peptide backbone and ammonium binding (239).
Figure 170: Anion sensor principle with 3-hydroxy-2-naphthanilide of Jiang et al.
Figure 171: 7-bromo-3-hydroxy-N-(2-hydroxyphenyl)naphthalene 2-carboxamide (241) and its amine binding.
Figure 172: Naturally occurring catechins with affinity to quaternary ammonium ions.
Figure 173: Spiropyran (244) and merocyanine form (244a) of the amino acid receptors of Fuji et al.
Figure 174: Coumarin aldehyde (245) and its iminium species with amino acid bound (245a) by Glass et al.
Figure 175: Coumarin aldehyde appended with boronic acid.
Figure 176: Quinolone aldehyde dimers by Glass et al.
Figure 177: Chromogenic ammonium ion receptors with trifluoroacetophenone recognition motifs.
Figure 178: Chromogenic ammonium ion receptor with trifluoroacetophenone recognition motif bound on different m...
Synthesis of mesogenic phthalocyanine-C60 donor–acceptor dyads designed for molecular heterojunction photovoltaic devices
- Yves Henri Geerts,
- Olivier Debever,
- Claire Amato and
- Sergey Sergeyev
Beilstein J. Org. Chem. 2009, 5, No. 49, doi:10.3762/bjoc.5.49
- /bjoc.5.49 Abstract A series of phthalocyanine-C60 dyads 2a–d was synthesized. Key steps in their synthesis are preparation of the low symmetry phthalocyanine intermediate by the statistical condensation of two phthalonitriles, and the final esterification of the fullerene derivative bearing a free COOH
- example of LC phthalocyanine-C60 dyads. Keywords: donor–acceptor dyad; fullerene; liquid crystals; phthalocyanine; phthalonitrile; Introduction Among sustainable energy technologies, photovoltaic (PV) conversion of solar energy is considered as a promising solution. Although currently the market is
- expect that for such high order of self-organization, liquid crystalline (LC) materials will be beneficial, because they combine order and fluidity, which allows the self-healing of structural defects [8]. One of the most widely used molecules in the bulk heterojunction PV devices is fullerene C60
Graphical Abstract
Figure 1: Phthalocyanine-C60 dyads 2a–d described in this paper, C60-derivative 1 (PCBM) and previously repor...
Scheme 1: Synthesis of low-symmetry phthalocyanines 4a–d.
Scheme 2: Synthesis of dyads 2a–d.
Figure 2: UV–vis absorption spectra of 2a (black), 4a (blue) and 1 (red) in CH2Cl2.
Figure 3: Cyclic voltammograms of 1 (red), 2a (grey), 2d (blue) and 3 (black) in CH2Cl2 (c = 10−4 M), scan ra...
Progress in liquid crystal chemistry
- Sabine Laschat
Beilstein J. Org. Chem. 2009, 5, No. 48, doi:10.3762/bjoc.5.48
- diverse topics such as phthalocyanine-fullerene hybrid materials for photovoltaic devices, functional metallomesogens, coaxial electrospinning of liquid crystal-containing microfibers, banana-discotic hybrid systems, ionic liquid crystals, relations between molecular length distribution and formation of
New diarylmethanofullerene derivatives and their properties for organic thin- film solar cells
- Daisuke Sukeguchi,
- Surya Prakash Singh,
- Mamidi Ramesh Reddy,
- Hideyuki Yoshiyama,
- Rakesh A. Afre,
- Yasuhiko Hayashi,
- Hiroki Inukai,
- Tetsuo Soga,
- Shuichi Nakamura,
- Norio Shibata and
- Takeshi Toru
Beilstein J. Org. Chem. 2009, 5, No. 7, doi:10.3762/bjoc.5.7
- -hexylthiophene) (P3HT) as the electron-donor and diarylmethanofullerene derivatives as the electron-acceptor material were examined. The {(methoxycarbonyl)phenyl[bis(octyloxy)phenyl]methano}fullerene showed power conversion efficiency as high as PCBM, but had higher solubility in a variety of organic solvents
- heterojunction solar cells; fullerene derivatives; high open-circuit voltage; Introduction Bulk heterojunction photovoltaic cells consisting of thin-film composites of conjugated polymers (donors) and fullerene derivatives (acceptors) are promising candidates for inexpensive, renewable solar energy conversion
- properties as acceptors, but it is still important to study the structure-efficiency relationship of the fullerene structure in order to develop highly efficient OPVs. The design of highly soluble derivatives of PCBM has also attracted much attention because 3D architectures such as vesicles and fibers are
Graphical Abstract
Figure 1: Diarylmethanofullerene derivatives.
Scheme 1: Synthesis of diarylmethanofullerene derivatives.
Figure 2: Device layout of the solar cell.
Figure 3: (A) J–V characteristics of the P3HT:1a-blended device annealed at 100–140 °C (black: 100 °C, red: 1...
Figure 4: (A) Spectral responsivity of the P3HT:1a-blended film on the ITO glass annealed at 100–140 °C (100 ...
Figure 5: The AFM images of the P3HT:1a- and P3HT:PCBM-blended films annealed at different temperatures. (A) ...
Synthesis of thienyl analogues of PCBM and investigation of morphology of mixtures in P3HT
- Fukashi Matsumoto,
- Kazuyuki Moriwaki,
- Yuko Takao and
- Toshinobu Ohno
Beilstein J. Org. Chem. 2008, 4, No. 33, doi:10.3762/bjoc.4.33
- methanofullerenes was performed by using dichloromethane as a solvent. es-TThCBM (3d) exhibited 1.4 times greater solubility in dichloromethane than PCBM. Keywords: fullerene; morphology; organic fullerenes; PCBM; photovoltaic cell; Introduction The demand for inexpensive, renewable energy sources continues to
- ]. Recently, bulk heterojunction solar cells consisting of a conjugated polymer (donor) and fullerene derivatives (acceptors) have inspired much scientific research owing to these reasons [8][9]. In this research, it has been demonstrated that the PV cells based on regio-regular poly(3-hexylthiophene) (P3HT
- exploring new acceptor materials have not been performed. In particular, there is no research focusing on how the structure of fullerene derivatives affects the morphology of the active layer of a PV device. However, it is essential to explore novel fullerene derivatives in order to achieve a significant
Graphical Abstract
Figure 1: Molecular structures of PCBM, ThCBM, MDMO-PPV, and P3HT.
Scheme 1: Synthesis of methanofullerenes (3a–d).
Figure 2: AFM phase images of P3HT/fullerene blend films containing (A) PCBM, (B) ThCBM, (C) 2-BThCBM (3a), a...
Figure 3: UV-Vis absorption spectra of P3HT/fullerene blend films for (A) PCBM, (B) ThCBM, (C) 2-BThCBM (3a),...
