- Deca-heterosubstituted corannulenes
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The Cu(i)-catalyzed Ullmann condensation reaction between aliphatic alcohols and sym-pentachlorocorannulene provides a convenient entry to 1,3,5,7,9-pentaalkoxycorannulenes. The latter are easily converted to novel deca-heterosubstituted derivatives, such as 1,3,5,7,9-penta-X-2,4,6,8,10-penta- Y-corannulenes by electrophilic aromatic substitution.
- Pogoreltsev, Alla,Solel, Ephrath,Pappo, Doron,Keinan, Ehud
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- 'Buckybowls' - Introducing curvature by solution phase synthesis
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New, non-pyrolytic methods are presented for the synthesis of curved-surface, polynuclear aromatic hydrocarbons related to the fullerenes. Tetrabromocorannulene is conveniently prepared on a large scale and then converted to corannulene, and also used as a synthon for further elaboration.
- Sygula, Andrzej,Xu, Guopin,Marcinow, Zbigniew,Rabideau, Peter W
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- Corannulene synthesis via the pyrolysis of silyl vinyl ethers
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The bis(trimethylsilyl enol ether) derived from 7,10-diacetylfluoranthene undergoes pyrolysis to afford corannulene. This is important in cases where the usual precursor, the bis(chlorovinyl) derivative, is not accessible from the diketone.
- Liu, Charlie Z.,Rabideau, Peter W.
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- Chemistry on the rim of buckybowls: Derivatization of 1,2,5,6-tetrabromocorannulene
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Synthesis of a number of substituted corannulenes and dibenzo[a,g]corannulenes starting from 1,2,5,6-tetrabromocorannulene 3 is described. Since 3 is conveniently obtained by a large scale, non-pyrolytic route, it may serve as a synthon for the further elaboration of this bowl-shaped system. (C) 2000 Elsevier Science Ltd.
- Xu,Sygula,Marcinow,Rabideau
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- Transition metal complexes in organic synthesis, part 55. Synthesis of corannulene via an iron-mediated [2+2+1] cycloaddition
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The synthesis of corannulene 2 in seven steps and 25% overall yield from 1,8-diiodonaphthalene 3 is reported.
- Knoelker, Hans-Joachim,Braier, Arnold,Broecher, Dirk J.,Jones, Peter G.,Piotrowski, Holger
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- Reversible phase transitions in a buckybowl monolayer
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Like penguins on ice, buckybowl molecules move closer together when cooled on a copper surface (see model of a corannulene molecule adsorbed on Cu(111)). Upon heating, the molecules spread out into the original crystal phase again. The lower density at ro
- Merz, Leo,Parschau, Manfred,Zoppi, Laura,Baldridge, Kim K.,Siegel, Jay S.,Ernst, Karl-Heinz
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- Non-pyrolytic syntheses of buckybowls: Corannulene, cyclopentacorannulene, and a semibuckminsterfullerene
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Corannulene (1), cyclopentacorannulene (2), and a C30H12 semibuckminsterfullerene (3) have been prepared by non-pyrolytic methods employing bromomethyl/dibromomethyl and/or dibromomethyl/dibromomethyl coupling with low-valent titanium or vanadium. Reductive coupling of tetrakis(dibromomethyl)-fluoranthene (8) with vanadium(III) chloride and lithium aluminum hydride affords corannulene in 70-75% yield. Similarly, hexakis(dibromomethyl)fluoranthene (13) leads to cyclopentacorannulene in 20-30% yield, and dodecabromo(octamethyl)indenofluoranthene (6) affords semibuckminsterfullerene (3) in 20% yield.
- Sygula, Andrzej,Rabideau, Peter W.
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- Emergent Self-Assembly of a Multicomponent Capsule via Iodine Capture
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Described here is a three-component self-assembly system that displays emergent behavior that differs from that of its constituents. The system comprises an all-hydrocarbon octaaryl macrocycle cyclo[8](1,3-(4,6-dimethyl)benzene (D4d-CDMB-8), corannulene (Cora), and I2. No appreciable interaction is seen between any pair of these three-components, either in cyclohexane or under various crystallization conditions. On the other hand, when all three-components are mixed in cyclohexane and allowed to undergo crystallization, a supramolecular iodine-containing capsule, ((D4d-CDMB-8)3(Cora)2)I2, is obtained. This all-hydrocarbon capsule consists of three D4d-CDMB-8 and two Cora subunits and contains a centrally bound I2 molecule as inferred from single-crystal and powder X-ray diffraction studies as well as solid-state 13C NMR and Raman spectroscopy. These analyses were complemented by solution-phase 1H NMR and UV-vis spectroscopic studies. No evidence of I2 escape from the capsule is seen, even at high temperatures (e.g., up to 418 K). The bound I2 is likewise protected from reaction with alkali or standard reductants in aqueous solution (e.g., saturated NaOH(aq) or aqueous Na2S2O3). It was also found that a mixed powder containing D4d-CDMB-8 and Cora in a 3:2 molar ratio could capture saturated I2 vapor or iodine from aqueous sources (e.g., 1.0 mM I2 in NaCl (35 wt %) or I2 + NaI(aq) (1.0 mM each)). The present system displays structural and functional features that go beyond what would be expected on the basis of a simple sum-of-the-components analysis. As such, it illustrates a new approach to creating self-assembled ensembles with emergent features.
- Yang, Yu-Dong,Chen, Xu-Lang,Sessler, Jonathan L.,Gong, Han-Yuan
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supporting information
p. 2315 - 2324
(2021/01/13)
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- Stack the Bowls: Tailoring the Electronic Structure of Corannulene-Integrated Crystalline Materials
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We report the first examples of purely organic donor–acceptor materials with integrated π-bowls (πBs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four-orders-of-magnitude conductivity enhancement in comparison with the parent framework. In addition to the first report of alkyne–azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual πB orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.
- Rice, Allison M.,Dolgopolova, Ekaterina A.,Yarbrough, Brandon J.,Leith, Gabrielle A.,Martin, Corey R.,Stephenson, Kenneth S.,Heugh, Rebecca A.,Brandt, Amy J.,Chen, Donna A.,Karakalos, Stavros G.,Smith, Mark D.,Hatzell, Kelsey B.,Pellechia, Perry J.,Garashchuk, Sophya,Shustova, Natalia B.
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supporting information
p. 11310 - 11315
(2018/08/11)
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- Electrochemically active porous organic polymers based on corannulene
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For the first time, porous organic polymers (POPs) based on the smallest buckybowl, corannulene (BB-POPs) have been synthesized. Three POPs were synthesised via Sonogashira co-polymerization of 1,2,5,6-tetrabromocorannulene and alkyne linkers. BB-POP-3 exhibits the highest surface area (SABET = 560 m2 g-1) and CO2 adsorption of 11.7 wt%, while they retain the redox properties of corannulene.
- Karunathilake, Arosha A.K.,Thompson, Christina M.,Perananthan, Sahila,Ferraris, John P.,Smaldone, Ronald A.
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supporting information
p. 12881 - 12884
(2016/11/06)
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- Superaromatic terpyridines based on corannulene responsive to metal ions
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Two superaromatic terpyridine ligands (1 and 2) incorporating a corannulene unit at the 4′-position are reported. The optical and metal sensing properties of both ligands were investigated by the naked eye, and UV-vis and fluorescence spectroscopy in this work. In 1, the corannulene motif is directly connected to the 4′-phenylterpyridine domain, while in 2, the corannulene motif and the 4′-phenylterpyridine domain are separated by an acetylene linker. Both 1 and 2 can work as chemosensors for metal ions and display different optical responses to various metal ions. It is shown that both ligands exhibit a colorimetric sensing ability for Fe2+ through an obvious color change from colorless to magenta, and this color change can be observed easily by the naked eye. The addition of Fe2+ also leads to significant changes in the absorption spectra of the ligands. A characteristic red shift in the emission spectra is observed in the presence of Zn 2+, which facilitates the discrimination of Zn2+ from other metal ions. In addition, density functional theory (DFT) and time-dependent-density functional theory (TD-DFT) calculations were performed and shown to be consistent with the observed experimental results. The Royal Society of Chemistry.
- Wu, Difeng,Shao, Tao,Men, Jian,Chen, Xiaochuan,Gao, Guowei
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supporting information
p. 1753 - 1761
(2014/01/06)
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- Kilogram-scale production of corannulene
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An efficient entry process for the synthesis of corannulene has been demonstrated on kilogram scale. Compared to the discovery and gram-scale syntheses, the amounts of solvents and reagents per gram of product were greatly reduced. Priority was given to implement the least toxic agents possible. Improvements in the purification of products obviated the need for column chromatography, alleviating four chromatographic operations. A new reduction method for the final step of the synthesis decreased reaction time from 6 to 0.5 days, and avoided the use of 100 equiv of zinc metal. The process now comprises nine steps, each of which runs smoothly at 100-L scale with a charging of 3-12 kg of educt. A total of 1.3 kg corannulene was isolated. This kilogram-scale process reduces material costs by over 2 orders of magnitude compared to that for the published gram-scale syntheses. Key opportunities in the process are identified for further improvements that should make synthesis on 100-kg scale feasible with a target price for 1 that is suitable for commercial production and engineering application.
- Butterfield, Anna M.,Gilomen, Bruno,Siegel, Jay S.
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experimental part
p. 664 - 676
(2012/08/07)
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- A combined experimental and theoretical study on the conformation of multiarmed chiral aryl ethers
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(Graph Presented) Four series of multiarmed chiral aryl ethers carrying two, three, five, or eight side-chains on a variety of aromatic core molecules (2-5) were prepared. The structure and conformation of 2 and 3 (in the solid state) were determined by the X-ray crystallographic analyses. While a pair of alternated (anti) conformers (i.e, up-down and down-up) were found in the crystal of 2, three side-arms in 3 were aligned in the same direction to give a C3-symmetric syn-conformation. Examinations by dispersion-corrected density functional (DFT-D) calculations revealed that two out of six anti- and two out of four syn-conformers of 2 are energetically most important. Two calculated structures of anti-conformers are in good agreement with those found in the solid state by X-ray analysis. Similarly, relevant conformations of syn-3, fully alternated 4, and C5-symmetric 5 were optimized at the DFT-D-B-LYP/TZVP level. The structure and conformation of the side-arms in 2-5 in solution were further studied by temperature dependent 1H NMR and UV-vis spectroscopy. In addition, comparative experimental and theoretical CD spectral studies were carried out in order to elucidate the contribution of the thermodynamically less-stable minor isomers in solution. The CD spectral changes observed for 2 and 3 at varying temperatures were quite different, while the parent chiral arene 1, as well as 4 and 5, only showed an increased intensity of the negative Cotton effect for the 1Lb band. The latter behavior is readily accounted for in terms of the conformational freezing of the chiral groups at low temperatures. The unusual CD spectral behavior observed for 2 and 3 was rationalized by the conformational alteration of the side-arms. Because of attractive van der Waals interactions between the aromatic units of the arms in nonpolar solvents, the syn-conformations become gradually more important for 2 at low temperatures, which eventually results in a weak positive Cotton effect for the 1Lb band. This was also supported by the SCS-MP2/TZVPP single-point energy calculations for the relevant conformers of 2. For 3, the contribution of the C3-symmetrical conformer becomes more important than the less-symmetrical isomers at low temperatures. The conformations of 2 and 3 in their excited states as well as in the oxidized states were also examined.
- Mori, Tadashi,Grimme, Stefan,Inoue, Yoshihisa
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p. 6998 - 7010
(2008/02/11)
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- On the coordination chemistry of corannulene, the smallest "buckybowl"
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A variety of methods, conventional and non-conventional, are used in attempts to prepare the compounds (η6-corannulene)M(CO) 3 (M = Cr, Mo, W), all unsuccessful. Conventional methods are also utilized in attempts to prepare the compound [CpFe(η6- corannulene)]PF6, but these result in mixtures of cationic CpFe(arene) complexes containing partially hydrogenated corannulene; similar results have been reported for other polyaromatic hydrocarbons. DFT calculations on the compound (η6-corannulene)Cr(CO)3 suggest that the (η6-corannulene)-Cr linkage is only a few kcal/mol weaker than the corresponding bond in (η6-benzene)Cr(CO)3, implying that failures in syntheses arise from kinetic, not thermodynamic problems.
- Stoddart, Michael W.,Brownie, John H.,Baird, Michael C.,Schmider, Hartmut L.
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p. 3440 - 3450
(2007/10/03)
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- Synthesis and Properties of Monosubstituted Ethynylcorannulenes
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The solution-phase synthesis of corannulene has been modified and it is now possible to prepare multi gram quantities of corannulene more efficiently, with considerably less toxic reagents. Cross-coupling of bromocorannulene with TMS-acetylene and phenylacetylene affords novel ethynyl-containing corannulene derivatives. Deprotection of TMS-ethynyl corannulene affords the naked alkyne, which can be cross-coupled with pentafluoroiodobenzene and bromocorannulene to afford the appropriate alkyne derivatives. The photophysical properties of this new and novel family of alkyne-containing corannulene derivatives has been evaluated and all of the new derivatives exhibit low to moderate quantum efficiencies.
- Jones, Carissa S.,Elliott, Eric,Siegel, Jay S.
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p. 187 - 191
(2007/10/03)
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- Addition of dihalocarbenes to corannulene. A fullerene-type reaction
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Dihalocarbenes (:CCl2, :CBr2, and :CI2) add preferentially to one of the radial double bonds of corannulene, rather than to the rim. These cyclopropanations strongly resemble the additions of dihalocarbenes to fullerenes, which likewise occur at 6:6-double bonds, destroy the cyclic conjugation in two adjacent benzene rings, and give 'closed' adducts. An explanation is offered for the abnormally high reactivity of the interior carbon atoms of corannulene. (C) 2000 Elsevier Science Ltd.
- Preda,Scott
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p. 9633 - 9637
(2007/10/03)
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- Synthesis of corannulene and alkyl derivatives of corannulene
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Synthesis of corannulene and alkyl corannulene derivatives has been accomplished using solution-phase chemistry. The key step in the synthesis is the coupling of benzylic bromides of 1,6,7,10-tetraalkylfluoranthene derivatives by low-valent titanium to construct the corannulene nucleus. The use of low-valent titanium represents a viable alternative to flash vacuum pyrolysis methods previously developed. Corannulene (1), methylcorannulene (8), three different dimethylcorannulenes (2, 3, 5), two different tetramethylcorannulenes (4, 6), acecorannulylene (7), C5h symmetric pentamethylcorannulene (9), and decamethylcorannulene (10) have been prepared using low-valent titanium carbon-carbon coupling chemistry and halogen for alkyl exchange chemistry mediated by trimethylaluminum and catalytic nickel salts.
- Seiders, T. Jon,Elliott, Eric L.,Grube, Gunther H.,Siegel, Jay S.
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p. 7804 - 7813
(2007/10/03)
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- Corannulene. A three-step synthesis
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Thermal cyclization of 7,10-diethynylfluoranthene (3) in the gas phase gives corannulene (2), the smallest bowl-shaped polycyclic hydrocarbon fragment of C60 with fullerene-like curvature. Bromocorannulene (10) and 1,6-dibromocorannulene (9) have also been obtained from flash pyrolysis of 7,10-bis(2,2-dibromovinyl)fluoranthene (8). Short, practical syntheses of several corannulene precursors from acenaphthenequinone are described which have made corannulene available in gram quantities.
- Scott, Lawrence T.,Cheng, Pei-Chao,Hashemi, Mohammed M.,Bratcher, Matthew S.,Meyer, Dayton T.,Warren, Hope B.
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p. 10963 - 10968
(2007/10/03)
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- A new synthesis of corannulene
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Flash vacuum pyrolysis of 2-substituted benzo[c]phenanthrene has been exploited as a pivotal step in a new, simple synthesis of the 'bowl-shaped' hydrocarbon corannulene 1.
- Mehta, Goverdhan,Panda, Gautam
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p. 2145 - 2148
(2007/10/03)
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- Cyclopentacorannulene: π-Facial stereoselective deuterogenation and determination of the bowl-to-bowl inversion barrier for a constrained buckybowl
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Attachment of an ethane or ethylene unit to the rim of corannulene produced relatively rigid bowls of dihydrocyclopenta- and cyclopentacorannulene, respectively. In contrast to the parent corannulenes, their inversion barriers are too high to be determined by the NMR coalescence methods. Due to the significant curvature of cyclopentacorannulene, deuterogenation is π-facial specific; both heterogeneous and homogeneous catalysis lead exclusively to exo-dideuteriocyclopentacorannulene 2a. Equilibration of the endo- and exo-isotopomers allowed the determination of ΔG? at 27.61-27.67 kcal/mol over the temperature range 52.1-99.3°C and the estimation of ΔH? (27.3 ± 0.7 kcal/mol) and ΔS? (-1.1 ± 0.2 eu) for the bowl-to-bowl inversion. The inversion barrier calculated at the HF/6-31G*//3-21G level (25.9 kcal/mol) compares well with the experimental result.
- Sygula, Andrzej,Abdourazak, Atteye H.,Rabideau, Peter W.
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p. 339 - 343
(2007/10/03)
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- Synthesis and Hydropyrolysis of Bis-trimethylsilyl Substituted 3-(4H-Cyclopentaphenanthrylidene)-1,4-pentadiyne. A New Route to Corannulene
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3-(4H-Cyclopentaphenanthrylidene)-1,5-bis-(trimethylsilyl)-1,4-pentadiyne (3) was synthesized and converted by hydropyrolysis into corannulene (1) besides others in reasonable yields.It represents a new route of the simplest bowl-shaped polycyclic aromatic hydrocarbon starting from an easily accessible precursor.
- Zimmermann, Gerhard,Nuechter, Uta,Hagen, Stefan,Nuechter, Matthias
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p. 4747 - 4750
(2007/10/02)
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