Hierarchic Supramolecular Interactions within Assemblies in Solution and in the Crystal of 2,3,6,7‐Tetrasubstituted 5,5′‐(Anthracene‐9,10‐diyl)bis[pyrimidin‐2‐amines]

Balaban, Teodor Silviu; Eichhöfer, Andreas; Krische, Michael J.; Lehn, Jean Marie

doi:10.1002/hlca.200690037

Cited by 13 publications

(12 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…2,3,6,7-tetrahydroxyanthraquinone (2,3,6,7-THAQ) was prepared using a previously reported synthetic route (15). The overall yield was 29% ( 1 H and 13 C NMR spectra shown in Fig.…”

Section: Chemical Characterization and Preparationmentioning

confidence: 99%

Alkaline quinone flow battery

Lin

Chen

Gerhardt

et al. 2015

Science

938

910

View full text Add to dashboard Cite

Abstract:Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of earth-abundant elements and are non-toxic, non-flammable, and safe for use in residential and commercial environments. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy. Main Text:The cost of photovoltaic (PV) and wind electricity has dropped so much that one of the largest barriers to getting the vast majority of our electricity from these renewable sources is their intermittency (1-3). Batteries provide a means to store electrical energy; however, traditional, enclosed batteries maintain discharge at peak power for far too short a duration to adequately regulate wind or solar power output (1, 2). In contrast, flow batteries can independently scale the power and energy components of the system by storing the electro-active species outside the battery container itself (3)(4)(5). In a flow battery, the power is generated in a device resembling a fuel cell, which contains electrodes separated by an ion-permeable membrane. Liquid solutions of redox-active species are pumped into the cell where they can be charged and discharged, before being returned to storage in an external storage tank. Scaling the amount of energy to be stored thus involves simply making larger tanks ( Fig 1A). Existing flow batteries are based on metal ions in acidic solution but there are challenges with corrosivity, hydrogen evolution, kinetics, material cost and abundance, and efficiency that thus far have prevented large-scale commercialization. The use of anthraquinones in an acidic aqueous flow battery can dramatically reduce battery costs (6, 7); however, the use of bromine in the other half of the system precludes deployment in residential communities due to toxicity concerns.We demonstrate that quinone-based flow batteries can be adapted to alkaline solutions, where hydroxylated anthraquinones are highly soluble and bromine can be replaced with the non-toxic ferricyanide ion (8, 9) -a food additive (10). Functionalization of 9,10-anthraquinone (AQ) with electron-donating groups such as OH has been shown to lower the reduction potential and expand the battery voltage (6). In alkaline solution, these OH groups are deprotonated to provide solubility and greater electron donation capability, which results in an increase in the open circuit voltage of 47% over the previously reported system. Because functionalization away from the ketone group provides molecules with the highest solubility...

show abstract

“…2,3,6,7-tetrahydroxyanthraquinone (2,3,6,7-THAQ) was prepared using a previously reported synthetic route (15). The overall yield was 29% ( 1 H and 13 C NMR spectra shown in Fig.…”

Section: Chemical Characterization and Preparationmentioning

confidence: 99%

Alkaline quinone flow battery

Lin

Chen

Gerhardt

et al. 2015

Science

938

910

View full text Add to dashboard Cite

show abstract

“…However, from SEC measurements at different concentrations and detection by RI the determination of the refractive index (RI) increment dn/dc is available comparing the deviation from respective PS standards. Using the d n / d c value measured for the employed polymers, it is possible to detect also by Multi Angle Light Scattering (MALS) (method see for example [ 23 ]) and to achieve more reliable molecular weight values for PIM-1 and the structural variations that are described in this study.…”

Section: Resultsmentioning

confidence: 99%

“…6 is easy to prepare, although in low yield (ca. 25%), from 1,2-dimethoxybenzene and pentanal following the synthesis described in [ 23 ] using pentanal instead of acetaldehyde. It shows good solubility in many common solvents, caused presumably by the butyl substitution in 9,10-position.…”

Section: Resultsmentioning

confidence: 99%

Membranes of Polymers of Intrinsic Microporosity (PIM-1) Modified by Poly(ethylene glycol)

2017

View full text Add to dashboard Cite

Until now, the leading polymer of intrinsic microporosity PIM-1 has become quite famous for its high membrane permeability for many gases in gas separation, linked, however, to a rather moderate selectivity. The combination with the hydrophilic and low permeable poly(ethylene glycol) (PEG) and poly(ethylene oxides) (PEO) should on the one hand reduce permeability, while on the other hand enhance selectivity, especially for the polar gas CO2 by improving the hydrophilicity of the membranes. Four different paths to combine PIM-1 with PEG or poly(ethylene oxide) and poly(propylene oxide) (PPO) were studied: physically blending, quenching of polycondensation, synthesis of multiblock copolymers and synthesis of copolymers with PEO/PPO side chain. Blends and new, chemically linked polymers were successfully formed into free standing dense membranes and measured in single gas permeation of N2, O2, CO2 and CH4 by time lag method. As expected, permeability was lowered by any substantial addition of PEG/PEO/PPO regardless the manufacturing process and proportionally to the added amount. About 6 to 7 wt % of PEG/PEO/PPO added to PIM-1 halved permeability compared to PIM-1 membrane prepared under similar conditions. Consequently, selectivity from single gas measurements increased up to values of about 30 for CO2/N2 gas pair, a maximum of 18 for CO2/CH4 and 3.5 for O2/N2.

show abstract

“…Anhydrous THF, toluene were distilled from sodium‐benzophenone immediately prior to use. The precursor 9,10‐dibromo‐2,3,6,7‐tetramethoxyanthracene ( 1 ) was prepared according to the literature . Column chromatography was performed on silica gel 60 (Merck 40–60 nm, 230–400 mesh).…”

Section: Methodsmentioning

confidence: 99%

Anthracene‐Fused Dibenzo[def,mno]chrysenes with a Helical Structure

et al. 2018

View full text Add to dashboard Cite

Scholl-type oxidative cyclodehydrogenation reactions were conducted for an anthryl-substituted dibenzo [def,mno]chrysene (DBC) precursor with the intention to prepare anthracene-fused DBCs with extended conjugation. The compound ADBC-1 with one cyclized ring and its two chloro-and oxy-derivatives (ADBC-Cl and ADBC-O) with good stability were successfully isolated and characterized. They showed largely red-shifted absorption spectra and amphoteric redox behavior. XRD analysis revealed that they can be regarded as large polycyclic aromatic hydrocarbons (PAHs) containing [5]helicene substructures with large twist angles of 67.8°-73.7°owing to steric congestion. Further cyclization to form newer CÀ C bonds failed, which can be explained by an open-shell diradical character and high HOMO energy levels of the products according to spinunrestricted DFT calculations. Results and Discussion SynthesisThe synthesis of the key intermediate ADBC was based on a Suzuki coupling-nucleophilic addition-Friedel-Crafts alkylationoxidative dehydrogenation strategy (Scheme 1). Compound 3 (9-bromo-10-mesityl-2,3,6,7-tetramethoxy-anthracene) was facilely synthesized in 49 % yield by Suzuki coupling reaction between excess of 9,10-dibromo-2,3,6,7-tetramethoxyanthra-[a] Q. ADBC-1 and Compound ADBC-Cl. 100 mg (0.0905 mmol) of ADBC was dissolved in 200 mL of anhydrous DCM in a dry reaction flask. Argon gas was purged into the reaction mixture throughout the reaction. A solution of 234.9 mg (1.4487 mmol) of anhydrous ferric chloride in 2 mL of nitromethane was charged into the reaction mixture through a syringe and stirred for 6 hrs at room temperature. Reaction was later quenched by 5 mL of water. Reaction mixture was later washed with 3 × 100 mL of water and the dichloromethane layer was collected and evaporated. The residue was purified by column chromatography (silica gel, DCM/Hexanes = 8 : 1, ADBC-Cl has larger polarity than ADBC-1) and preparative thin-layer chromatography (TLC) to afford ADBC-1 and ADBC-Cl as dark green solids (58.9 mg, 59 % for ADBC-1, and 26.8 mg, 26 % for ADBC-Cl). ADBC-1: 1 H NMR (400 MHz, CD 2 Cl 2 , ppm): δ = 9.66 (d, J = 8.1 Hz, 1H), 8.35 (d, J = 8.2 Hz 1H), 8.13 (d, J = 7.2 Hz, 1H), 8.02-7.96 (m, 2H), 7.81 (t, J = 7.8 Hz, 1H), 7.76 (d, J = 9.3 Hz, 1H), 7.67 (d, J = 8.4 Hz, 1H), 7.56 (d, J = 9.1 Hz, 1H), 7.20-4 5 6 7 8

show abstract

Hierarchic Supramolecular Interactions within Assemblies in Solution and in the Crystal of 2,3,6,7‐Tetrasubstituted 5,5′‐(Anthracene‐9,10‐diyl)bis[pyrimidin‐2‐amines]

Cited by 13 publications

References 31 publications

Alkaline quinone flow battery

Alkaline quinone flow battery

Membranes of Polymers of Intrinsic Microporosity (PIM-1) Modified by Poly(ethylene glycol)

Anthracene‐Fused Dibenzo[def,mno]chrysenes with a Helical Structure

Contact Info

Product

Resources

About