scholarly journals Light Directs Monomer Coordination in Catalyst-Free Grignard Photopolymerization

2021 ◽  
Author(s):  
Eliot Woods ◽  
Alexandra Berl ◽  
Leanna Kantt ◽  
Christopher Eckdahl ◽  
Michael Wasielewski ◽  
...  
Keyword(s):  
Conjugated Polymers ◽  
Radical Anion ◽  
Elevated Temperatures ◽  
Spectroscopic Studies ◽  
Computational Investigation ◽  
Catalyst Free ◽  
Active Layers ◽  
End Groups ◽  
Type Coupling

π-Conjugated polymers can serve as active layers in flexible and lightweight electronics, and are conventionally synthesized by transition-metal-mediated polycondensation at elevated temperatures. We recently reported a photopolymerization of electron-deficient heteroaryl Grignard monomers that enables the catalyst-free synthesis of n-type π-conjugated polymers. Herein we provide an experimental and computational investigation of the mechanism of this photopolymerization. Spectroscopic studies performed <i>in situ</i> and after quenching reveal that the propagating species is a radical anion with halide end groups. DFT calculations for model oligomers suggest a Mg-templated S<sub>RN</sub>1-type coupling, in which Grignard monomer coordination to the radical anion chain avoids the formation of free sp<sup>2</sup> radicals and enables C–C bond formation with very low barriers. We find that light plays an unusual role in the reaction, photoexciting the radical anion chain to shift electron density to the termini and thus favor productive monomer binding.

Light Directs Monomer Coordination in Catalyst-Free Grignard Photopolymerization

2021 ◽  
Author(s):  
Eliot Woods ◽  
Alexandra Berl ◽  
Leanna Kantt ◽  
Michael Wasielewski ◽  
Brandon E. Haines ◽  
...  
Keyword(s):  
Conjugated Polymers ◽  
Radical Anion ◽  
Elevated Temperatures ◽  
Spectroscopic Studies ◽  
Computational Investigation ◽  
Catalyst Free ◽  
Active Layers ◽  
End Groups ◽  
Type Coupling

π-Conjugated polymers can serve as active layers in flexible and lightweight electronics, and are conventionally synthesized by transition-metal-mediated polycondensation at elevated temperatures. We recently reported a photopolymerization of electron-deficient heteroaryl Grignard monomers that enables the catalyst-free synthesis of n-type π-conjugated polymers. Herein we provide an experimental and computational investigation of the mechanism of this photopolymerization. Spectroscopic studies performed <i>in situ</i> and after quenching reveal that the propagating species is a radical anion with halide end groups. DFT calculations for model oligomers suggest a Mg-templated S<sub>RN</sub>1-type coupling, in which Grignard monomer coordination to the radical anion chain avoids the formation of free sp<sup>2</sup> radicals and enables C–C bond formation with very low barriers. We find that light plays an unusual role in the reaction, photoexciting the radical anion chain to shift electron density to the termini and thus favor productive monomer binding.

Light Directs Monomer Coordination in Catalyst-Free Grignard Photopolymerization

2021 ◽  
Author(s):  
Eliot Woods ◽  
Alexandra Berl ◽  
Leanna Kantt ◽  
Michael Wasielewski ◽  
Brandon E. Haines ◽  
...  
Keyword(s):  
Conjugated Polymers ◽  
Radical Anion ◽  
Elevated Temperatures ◽  
Spectroscopic Studies ◽  
Computational Investigation ◽  
Catalyst Free ◽  
Active Layers ◽  
End Groups ◽  
Type Coupling

π-Conjugated polymers can serve as active layers in flexible and lightweight electronics, and are conventionally synthesized by transition-metal-mediated polycondensation at elevated temperatures. We recently reported a photopolymerization of electron-deficient heteroaryl Grignard monomers that enables the catalyst-free synthesis of n-type π-conjugated polymers. Herein we provide an experimental and computational investigation of the mechanism of this photopolymerization. Spectroscopic studies performed <i>in situ</i> and after quenching reveal that the propagating species is a radical anion with halide end groups. DFT calculations for model oligomers suggest a Mg-templated S<sub>RN</sub>1-type coupling, in which Grignard monomer coordination to the radical anion chain avoids the formation of free sp<sup>2</sup> radicals and enables C–C bond formation with very low barriers. We find that light plays an unusual role in the reaction, photoexciting the radical anion chain to shift electron density to the termini and thus favor productive monomer binding.

Controlling Defects in Double-Layer Cuprates by Chemical Modifications

1996 ◽  
Vol 453 ◽  
Author(s):  
P. A Salvador ◽  
K. B. Greenwood ◽  
K. Otzschi ◽  
J. W Koenitzer ◽  
B. M. Dabrowski ◽  
...  
Keyword(s):  
Electrical Conductivity ◽  
High Temperature ◽  
Oxygen Partial Pressure ◽  
Partial Pressure ◽  
Transport Properties ◽  
Elevated Temperatures ◽  
Double Perovskite ◽  
Chemical Modifications ◽  
Active Layers

AbstractIn-situ high temperature electrical conductivity and thermopower have been measured simultaneously on a number of ordered perovskite-like oxides containing double CUO4/2 sheets. Equilibrium measurements have been conducted as a function of oxygen partial pressure, temperature and chemical substitution in order to understand the relationships between the chemical architecture and the transport and defect properties. Data for LaBa2Cu2NbO8 and LaCa2Cu2GaO7 are presented and compared with those of known triple perovskite superconductors, Y1−xCaxSr2Cu2GaO7 and YBa2Cu3O7−δ, and several quadruple perovskites, Ln′Ln″Ba2Cu2M2O11 (Ln = Lanthanide, Y; M = Sn, Ti). These materials belong to a general family of superconductors which are constructed from similar ‘active’ layers (double perovskite blocks of square-pyramidal copper-oxygen sheets), and interleaved with fixed valence cations in perovskite-like ‘conditioning’ layers. Similarities in the transport properties of the non-superconducting and superconducting materials at elevated temperatures are illustrated, and the amount and types of defects, including carrier concentrations, are correlated with the internal chemistry and inner architecture of each material.

Electron and ion irradiation-induced dissolution of mechanical twins in the intermetalic U3Si: An in situ HVEM study

1989 ◽  
Vol 47 ◽  
pp. 652-653
Author(s):  
Charles W. Allen ◽  
Robert C. Birtcher
Keyword(s):  
Elevated Temperatures ◽  
Ion Irradiation ◽  
Ion Beam ◽  
National Laboratory ◽  
Argonne National Laboratory ◽  
Heavy Ion ◽  
High Energy ◽  
Mechanical Twinning ◽  
In Situ Experiments

The uranium silicides, including U3Si, are under study as candidate low enrichment nuclear fuels. Ion beam simulations of the in-reactor behavior of such materials are performed because a similar damage structure can be produced in hours by energetic heavy ions which requires years in actual reactor tests. This contribution treats one aspect of the microstructural behavior of U3Si under high energy electron irradiation and low dose energetic heavy ion irradiation and is based on in situ experiments, performed at the HVEM-Tandem User Facility at Argonne National Laboratory. This Facility interfaces a 2 MV Tandem ion accelerator and a 0.6 MV ion implanter to a 1.2 MeV AEI high voltage electron microscope, which allows a wide variety of in situ ion beam experiments to be performed with simultaneous irradiation and electron microscopy or diffraction.At elevated temperatures, U3Si exhibits the ordered AuCu3 structure. On cooling below 1058 K, the intermetallic transforms, evidently martensitically, to a body-centered tetragonal structure (alternatively, the structure may be described as face-centered tetragonal, which would be fcc except for a 1 pet tetragonal distortion). Mechanical twinning accompanies the transformation; however, diferences between electron diffraction patterns from twinned and non-twinned martensite plates could not be distinguished.

The threshold energy for atom displacement in fcc metals

1990 ◽  
Vol 48 (4) ◽  
pp. 530-531
Author(s):  
Wilfried Sigle ◽  
Matthias Hohenstein ◽  
Alfred Seeger
Keyword(s):  
Growth Rate ◽  
Elevated Temperatures ◽  
Threshold Energy ◽  
Dislocation Loops ◽  
Absolute Minimum ◽  
Voltage Electron ◽  
Atom Displacement ◽  
Electron Microscopes ◽  
Fcc Metal

Prolonged electron irradiation of metals at elevated temperatures usually leads to the formation of large interstitial-type dislocation loops. The growth rate of the loops is proportional to the total cross-section for atom displacement,which is implicitly connected with the threshold energy for atom displacement, Ed . Thus, by measuring the growth rate as a function of the electron energy and the orientation of the specimen with respect to the electron beam, the anisotropy of Ed can be determined rather precisely. We have performed such experiments in situ in high-voltage electron microscopes on Ag and Au at 473K as a function of the orientation and on Au as a function of temperature at several fixed orientations.Whereas in Ag minima of Ed are found close to <100>,<110>, and <210> (13-18eV), (Fig.1) atom displacement in Au requires least energy along <100>(15-19eV) (Fig.2). Au is thus the first fcc metal in which the absolute minimum of the threshold energy has been established not to lie in or close to the <110> direction.

In Situ Polymerized Protic Ionogels for Fuel Cells at Elevated Temperatures

2021 ◽  
Author(s):  
Mengdou Zou ◽  
Jie Luo ◽  
Xurui Wang ◽  
Shuai Tan ◽  
Caihong Wang ◽  
...  
Keyword(s):  
Fuel Cells ◽  
Elevated Temperatures

scholarly journals Ultraviolet Absorption Cross-Sections of Ammonia at Elevated Temperatures for Nonintrusive Quantitative Detection in Combustion Environments

2021 ◽  
pp. 000370282199044
Author(s):  
Wubin Weng ◽  
Shen Li ◽  
Marcus Aldén ◽  
Zhongshan Li
Keyword(s):  
Cross Section ◽  
Cross Sections ◽  
Absorption Cross Section ◽  
Elevated Temperatures ◽  
Uv Absorption ◽  
Energy Utilization ◽  
Quantitative Detection ◽  
Absorption Cross ◽  
Hot Gas

Ammonia (NH3) is regarded as an important nitrogen oxides (NOx) precursor and also as an effective reductant for NOx removal in energy utilization through combustion, and it has recently become an attractive non-carbon alternative fuel. To have a better understanding of thermochemical properties of NH3, accurate in situ detection of NH3 in high temperature environments is desirable. Ultraviolet (UV) absorption spectroscopy is a feasible technique. To achieve quantitative measurements, spectrally resolved UV absorption cross-sections of NH3 in hot gas environments at different temperatures from 295 K to 590 K were experimentally measured for the first time. Based on the experimental results, vibrational constants of NH3 were determined and used for the calculation of the absorption cross-section of NH3 at high temperatures above 590 K using the PGOPHER software. The investigated UV spectra covered the range of wavelengths from 190 nm to 230 nm, where spectral structures of the [Formula: see text] transition of NH3 in the umbrella bending mode, v2, were recognized. The absorption cross-section was found to decrease at higher temperatures. For example, the absorption cross-section peak of the (6, 0) vibrational band of NH3 decreases from ∼2 × 10−17 to ∼0.5 × 10−17 cm2/molecule with the increase of temperature from 295 K to 1570 K. Using the obtained absorption cross-section, in situ nonintrusive quantification of NH3 in different hot gas environments was achieved with a detection limit varying from below 10 parts per million (ppm) to around 200 ppm as temperature increased from 295 K to 1570 K. The quantitative measurement was applied to an experimental investigation of NH3 combustion process. The concentrations of NH3 and nitric oxide (NO) in the post flame zone of NH3–methane (CH4)–air premixed flames at different equivalence ratios were measured.

Insertion Reaction of 2-Halo-N-allylanilines with K2S Involving Trisulfur Radical Anion: Synthesis of Benzothiazole Derivatives under Transition-Metal-Free Conditions

Synthesis ◽  
2020 ◽  
Author(s):  
Yan-Wei Zhao ◽  
Shun-Yi Wang ◽  
Xin-Yu Liu ◽  
Tian Jiang ◽  
Weidong Rao
Keyword(s):  
Transition Metal ◽  
Radical Anion ◽  
Radical Cyclization ◽  
Transition Metal Catalysis ◽  
Insertion Reaction ◽  
Metal Catalysis ◽  
Metal Free ◽  
Benzothiazole Derivatives

AbstractA synthesis of benzothiazole derivatives through the reaction of 2-halo-N-allylanilines with K2S in DMF is developed. The trisulfur radical anion S3·–, which is generated in situ from K2S in DMF, initiates the reaction without transition-metal catalysis or other additives. In addition, two C–S bonds are formed and heteroaromatization of benzothiazole is triggered by radical cyclization and H-shift.

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