146885-82-7Relevant academic research and scientific papers
Selective Synthesis of Perfluoroalkylated Corannulenes and Investigation of their Structural, Dynamic and Electrochemical Behavior
Haupt, Axel,Keller, Lisa-Marie,Kutter, Maximilian,Lentz, Dieter
, p. 10756 - 10765 (2018)
Herein we report general methods allowing the synthesis of various perfluoroalkylated corannulenes with a specific substitution pattern. Variable temperature NMR spectroscopic investigations revealed dynamic behavior which was analyzed by line shape analysis. The activation parameters of these dynamic processes were determined. For a tetrasubstituted compound it was possible to observe through space scalar coupling. The packing motifs were elucidated by X-ray crystallography, showing that the substitution pattern as well as the size of substituents strongly influence intermolecular π-stacking. The reduction potentials of the perfluoroalkylated compounds were determined by cyclic voltammetry.
Stack the Bowls: Tailoring the Electronic Structure of Corannulene-Integrated Crystalline Materials
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.
supporting information, p. 11310 - 11315 (2018/08/11)
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.
Hierarchical Corannulene-Based Materials: Energy Transfer and Solid-State Photophysics
Rice, Allison M.,Fellows, W. Brett,Dolgopolova, Ekaterina A.,Greytak, Andrew B.,Vannucci, Aaron K.,Smith, Mark D.,Karakalos, Stavros G.,Krause, Jeanette A.,Avdoshenko, Stanislav M.,Popov, Alexey A.,Shustova, Natalia B.
supporting information, p. 4525 - 4529 (2017/04/11)
We report the first example of a donor–acceptor corannulene-containing hybrid material with rapid ligand-to-ligand energy transfer (ET). Additionally, we provide the first time-resolved photoluminescence (PL) data for any corannulene-based compounds in the solid state. Comprehensive analysis of PL data in combination with theoretical calculations of donor–acceptor exciton coupling was employed to estimate ET rate and efficiency in the prepared material. The ligand-to-ligand ET rate calculated using two models is comparable with that observed in fullerene-containing materials, which are generally considered for molecular electronics development. Thus, the presented studies not only demonstrate the possibility of merging the intrinsic properties of π-bowls, specifically corannulene derivatives, with the versatility of crystalline hybrid scaffolds, but could also foreshadow the engineering of a novel class of hierarchical corannulene-based hybrid materials for optoelectronic devices.
Kilogram-scale production of corannulene
Butterfield, Anna M.,Gilomen, Bruno,Siegel, Jay S.
, p. 664 - 676 (2012/08/07)
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.
Self-assembly of fivefold-symmetric molecules on a threefold-symmetric surface
Guillermet, Olivier,Niemi, Eeva,Nagarajan, Samuthira,Bouju, Xavier,Martrou, David,Gourdon, Andre,Gauthier, Sebastien
supporting information; experimental part, p. 1970 - 1973 (2009/07/25)
Buckybowls: The adsorption of penta-tert-butylcorannulene, a molecule with fivefold symmetry, on Cu(111), a surface with threefold symmetry, is investigated by scanning tunneling microscopy complemented by structure calculations. The symmetry mismatch is
Synthesis of corannulene and alkyl derivatives of corannulene
Seiders, T. Jon,Elliott, Eric L.,Grube, Gunther H.,Siegel, Jay S.
, p. 7804 - 7813 (2007/10/03)
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.
1,6,7,10-Tetramethylfluoranthene: Synthesis and Structure of a Twisted Polynuclear Aromatic Hydrocarbon
Borchardt, Allen,Hardcastle, Kenneth,Gantzel, Peter,Siegel, Jay S.
, p. 273 - 276 (2007/10/02)
The structure and synthesis of the overcrowded polynuclear aromatic 1,6,7,10-tetramethylfluoranthene, 1, is presented.The structures of 1 and 11 have been determined by X-ray diffraction to be twisted into conformations of approximately C2 symmetry due to the buttressing of the flanking methyl groups.Semi-empirical calculations (AM1) on 1 find two minima, twist and fold; the twist is of lower energy.The energy for enantiomerization of 1 is set at below 7.0 kcal/mol by variable temperature NMR.Computations predict a likely path to account for the ribbon twist.
