Synthesis and antiaromatic character of alkyl-substituted di-peri-dinaphthoporphyrin Ni(II) complex

2017 ◽  
Vol 21 (12) ◽  
pp. 850-856 ◽  
Author(s):  
Masataka Umetani ◽  
Koji Naoda ◽  
Takayuki Tanaka ◽  
Atsuhiro Osuka
Keyword(s):  
Cyclic Voltammetry ◽  
Solid State ◽  
Potential Difference ◽  
Planar Structure ◽  
H Nmr ◽  
Antiaromatic Character ◽  
Homo Lumo ◽  
Nmr Signals

Antiaromatic molecules have recently been proven to display unique properties such as small HOMO–LUMO gaps, ambipolar carrier transporting and [Formula: see text]-stack-induced aromatic stabilizations. These intriguing properties have been demonstrated by stable antiaromatic molecules that exhibit a distinct antiaromatic character. Di-peri-dinaphthoporphyrins are peripherally [Formula: see text]-extended porphyrinoids that exhibit a planar structure and a distinct antiaromatic character stemming from their 24[Formula: see text] electron circuit. Herein, we report an alkyl-substituted di-peri-dinaphthoporphyrin Ni(II) complex 5Ni bearing less peripheral bulkiness as compared with phenyl-substituted ones. 5Ni displayed upfield-shifted [Formula: see text]H NMR signals due to [Formula: see text]-protons, indicating its distinct antiaromaticity, and a slightly shorter intermolecular packing distance (ca. 3.402 Å) in the solid state. Cyclic voltammetry shows a larger potential difference between the first and second oxidation waves, implying that this molecule tends to stack favorably in its oxidized state.

Experimental Assessment of the Practical Oxidative Stability of Lithium Thiophosphate Solid Electrolytes

2019 ◽  
Author(s):  
Georg Dewald ◽  
Saneyuki Ohno ◽  
Marvin Kraft ◽  
Raimund Koerver ◽  
Paul Till ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Solid State ◽  
Oxidative Stability ◽  
Photoelectron Spectroscopy ◽  
Solid Electrolytes ◽  
Stability Limit ◽  
Lithium Ion ◽  
High Energy ◽  
Redox Activity ◽  
Solid State Batteries

<p>All-solid-state batteries are often expected to replace conventional lithium-ion batteries in the future. However, the practical electrochemical and cycling stability of the best-conducting solid electrolytes, i.e. lithium thiophosphates, are still critical issues that prevent long-term stable high-energy cells. In this study, we use <i>stepwise</i><i>cyclic voltammetry </i>to obtain information on the practical oxidative stability limit of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub>, a Li<sub>2</sub>S‑P<sub>2</sub>S<sub>5</sub>glass, as well as the argyrodite Li<sub>6</sub>PS<sub>5</sub>Cl solid electrolytes. We employ indium metal and carbon black as the counter and working electrode, respectively, the latter to increase the interfacial contact area to the electrolyte as compared to the commonly used planar steel electrodes. Using a stepwise increase in the reversal potentials, the onset potential at 25 °C of oxidative decomposition at the electrode-electrolyte interface is identified. X‑ray photoelectron spectroscopy is used to investigate the oxidation of sulfur(-II) in the thiophosphate polyanions to sulfur(0) as the dominant redox process in all electrolytes tested. Our results suggest that after the formation of these decomposition products, significant redox behavior is observed. This explains previously reported redox activity of thiophosphate solid electrolytes, which contributes to the overall cell performance in solid-state batteries. The <i>stepwise cyclic voltammetry</i>approach presented here shows that the practical oxidative stability at 25 °C of thiophosphate solid electrolytes against carbon is kinetically higher than predicted by thermodynamic calculations. The method serves as an efficient guideline for the determination of practical, kinetic stability limits of solid electrolytes. </p>

Experimental Assessment of the Practical Oxidative Stability of Lithium Thiophosphate Solid Electrolytes

2019 ◽  
Author(s):  
Georg Dewald ◽  
Saneyuki Ohno ◽  
Marvin Kraft ◽  
Raimund Koerver ◽  
Paul Till ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Solid State ◽  
Oxidative Stability ◽  
Photoelectron Spectroscopy ◽  
Solid Electrolytes ◽  
Stability Limit ◽  
Lithium Ion ◽  
High Energy ◽  
Redox Activity ◽  
Solid State Batteries

<p>All-solid-state batteries are often expected to replace conventional lithium-ion batteries in the future. However, the practical electrochemical and cycling stability of the best-conducting solid electrolytes, i.e. lithium thiophosphates, are still critical issues that prevent long-term stable high-energy cells. In this study, we use <i>stepwise</i><i>cyclic voltammetry </i>to obtain information on the practical oxidative stability limit of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub>, a Li<sub>2</sub>S‑P<sub>2</sub>S<sub>5</sub>glass, as well as the argyrodite Li<sub>6</sub>PS<sub>5</sub>Cl solid electrolytes. We employ indium metal and carbon black as the counter and working electrode, respectively, the latter to increase the interfacial contact area to the electrolyte as compared to the commonly used planar steel electrodes. Using a stepwise increase in the reversal potentials, the onset potential at 25 °C of oxidative decomposition at the electrode-electrolyte interface is identified. X‑ray photoelectron spectroscopy is used to investigate the oxidation of sulfur(-II) in the thiophosphate polyanions to sulfur(0) as the dominant redox process in all electrolytes tested. Our results suggest that after the formation of these decomposition products, significant redox behavior is observed. This explains previously reported redox activity of thiophosphate solid electrolytes, which contributes to the overall cell performance in solid-state batteries. The <i>stepwise cyclic voltammetry</i>approach presented here shows that the practical oxidative stability at 25 °C of thiophosphate solid electrolytes against carbon is kinetically higher than predicted by thermodynamic calculations. The method serves as an efficient guideline for the determination of practical, kinetic stability limits of solid electrolytes. </p>

scholarly journals 13C and 1H NMR Spectra of Synthetic (25R)-5α-Spirostanes

1999 ◽  
Vol 23 (1) ◽  
pp. 48-49
Author(s):  
Martín A. Iglesias Arteaga ◽  
Carlos S. Pérez Martinez ◽  
Roxana Pérez Gil ◽  
Francisco Coll Manchado
Keyword(s):  
1H Nmr ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
1H Nmr Spectra ◽  
H Nmr ◽  
C 23 ◽  
Main Effects ◽  
Nmr Signals

The assignment of 13C and 1H NMR signals of synthetic (25 R)-5α-spirostanes is presented; the main effects on chemical shifts due to substitution at C-23 are briefly discussed.

scholarly journals Unusual piezochromic fluorescence of a distyrylpyrazine derivative crystals: phase transition through [2 + 2] photocycloaddition under UV irradiation

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Young-Jae Jin ◽  
Hyosang Park ◽  
Byung-Chun Moon ◽  
Jae Hong Kim ◽  
Wang-Eun Lee ◽  
...  
Keyword(s):  
Phase Transition ◽  
Solid State ◽  
Uv Irradiation ◽  
Mechanical Grinding ◽  
Green Color ◽  
H Nmr ◽  
Uv Visible ◽  
Stacking Structure ◽  
Orange Color ◽  
Molecular Stacking

AbstractThe piezochromic fluorescence (FL) of a distyrylpyrazine derivative, 2,3-diisocyano-5,6-distyrylpyrazine (DSP), was investigated in this study. Depending on the recrystallization method, DSP afforded two different crystals with green and orange FL emission. The orange color FL emission crystal (O-form) was easily converted to the green color FL emission one (G-form) by manual grinding. The G-form was also converted to a slightly different orange color FL emission crystal (RO-form) by a weak UV irradiation. When the RO-form was ground again, the G-form was regenerated. The FL colors changed between the G- and RO-forms over several ten times by repeated mechanical grinding and UV irradiation. The FL, UV–visible, 1H-NMR and XRD results showed that the O (or RO)-to-G transformation induced by mechanical stress results from the change of degree of molecular stacking from dense molecular stacking structure to relatively loose molecular stacking structure, whereas the G-to-RO reconversion by UV irradiation results from return to dense molecular stacking structure again due to lattice movement (lattice slipping) allowed by photocycloaddition in solid-state.

scholarly journals Oligosilanylated Silocanes

Molecules ◽  
2021 ◽  
Vol 26 (1) ◽  
pp. 244
Author(s):  
Mohammad Aghazadeh Meshgi ◽  
Alexander Pöcheim ◽  
Judith Baumgartner ◽  
Viatcheslav V. Jouikov ◽  
Christoph Marschner
Keyword(s):  
Cyclic Voltammetry ◽  
Solid State ◽  
Xrd Analysis ◽  
29Si Nmr ◽  
Single Crystal Xrd ◽  
Substitution Pattern ◽  
Silyl Group ◽  
Steric Factors ◽  
Single Crystal Xrd Analysis ◽  
29Si Nmr Spectroscopy

A number of mono- and dioligosilanylated silocanes were prepared. Compounds included silocanes with 1-methyl-1-tris(trimethylsilyl)silyl, 1,1-bis[tris(trimethylsilyl)silyl], and 1,1-bis[tris(trimethylsilyl)germyl] substitution pattern as well as two examples where the silocane silicon atom is part of a cyclosilane or oxacyclosilane ring. The mono-tris(trimethylsilyl)silylated compound could be converted to the respective silocanylbis(trimethylsilyl)silanides by reaction with KOtBu and in similar reactions the cyclosilanes were transformed to oligosilane-1,3-diides. However, the reaction of the 1,1-bis[tris(trimethylsilyl)silylated] silocane with two equivalents of KOtBu leads to the replacement of one tris(trimethylsilyl)silyl unit with a tert-butoxy substituent followed by silanide formation via KOtBu attack at one of the SiMe3 units of remaining tris(trimethylsilyl)silyl group. For none of the silylated silocanes, signs of hypercoordinative interaction between the nitrogen and silicon silocane atoms were detected either in the solid state. by single crystal XRD analysis, nor in solution by 29Si-NMR spectroscopy. This was further confirmed by cyclic voltammetry and a DFT study, which demonstrated that the N-Si distance in silocanes is not only dependent on the energy of a potential N-Si interaction, but also on steric factors and through-space interactions of the neighboring groups at Si and N, imposing the orientation of the pz(N) orbital relative to the N-Si-X axis.

Synthesis and Characterization of a Methanofullerene-4-Fluoro-α-Cyanostilbene Dyad as a Potential Acceptor for Organic Solar Cells

2015 ◽  
Vol 1784 ◽  
Author(s):  
Venkata Neti
Keyword(s):  
Mass Spectrometry ◽  
Cyclic Voltammetry ◽  
Solar Cells ◽  
Organic Solar Cells ◽  
Synthesis And Characterization ◽  
Lumo Energy ◽  
Homo Lumo ◽  
Aryl Ester

ABSTRACTA series of fluorine appended highly conjugated fullerenes were prepared containing fluoro-α-cyanostilbene and aryl ester units. These modified PCBM dyads are fully characterized by NMR, Mass spectrometry, UV-vis, and cyclic voltammetry (Figures 1-4). It was found that the presence of fluoro-α-cyanostilbenes and esters affects the cyclic voltammetry and absorption in the UV-Vis region. The PCBA modified fullerenes significantly influences the HOMO-LUMO energy and wide absorption compared to PCBM.

Electrochemically Synthesis and Characterization of Copolymers Based on 1, 4-Diethoxybenzene and 3, 4-Ethylenedioxythiophene

2011 ◽  
Vol 335-336 ◽  
pp. 989-993
Author(s):  
Mi Ouyang ◽  
Zhen Wei Yu ◽  
Yi Xu ◽  
Yu Jian Zhang ◽  
Cheng Zhang
Keyword(s):  
Cyclic Voltammetry ◽  
Ir Spectroscopy ◽  
Feed Ratio ◽  
Synthesis And Characterization ◽  
Monomer Mixture ◽  
Long Wavelength ◽  
H Nmr ◽  
Ft Ir ◽  
Ft Ir Spectroscopy

Copolymers based on 1, 4-diethoxybenzene (DEB) and 3, 4-ethylenedioxythiophene (EDOT) were electrochemically synthesized and characterized. The structures of the copolymers were established by 1H NMR and FT-IR spectroscopy. The results indicated the final product was a copolymer instead of a blend or a composite. The physical properties were systematically investigated by cyclic voltammetry, UV-vis absorption and fluorescence. The PL maximum of copolymers presented obviously red-shift to long wavelength as the feed ratio of EDOT in monomer mixture increased.

Synthesis, Characterization and Photophysical Properties of Rhenium(I) Complexe with 2-(naphthalen-2-yl)-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline

2014 ◽  
Vol 988 ◽  
pp. 66-69
Author(s):  
Qiang Li ◽  
Le Li ◽  
Rong Feng Zhong ◽  
Hai Di Cai ◽  
Feng Zhao
Keyword(s):  
Experimental Data ◽  
Solid State ◽  
Photophysical Properties ◽  
Broad Band ◽  
High Energy ◽  
H Nmr ◽  
Emission Maximum ◽  
Broad Band Emission ◽  
Band Emission

In this paper, a Re(I) complex [Re(CO)3(E2)Cl], where E2 = 2-(naphthalen-2-yl)-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline(E2), was synthesized and characterized by 1H NMR successfully. Experimental data confirm that Re(I) complex [Re(CO)3(E2)Cl] is high-energy-emitting one. The broad band emission upon excitation at λ = 400 nm with the emission maximum locates at λ = 581 nm in solid state and 614nm in CH2Cl2 solution were observed.

scholarly journals Synthesis of a One-Dimensional Coordination Polymer of Nickel(II) Complex with a β-Oxodithioester Ligand

2017 ◽  
Vol 2017 ◽  
pp. 1-7
Author(s):  
Ricardo Rosas-Reyes ◽  
Yasmi Reyes-Ortega ◽  
T. Jesus Morales-Juarez ◽  
Virginia Gómez-Vidales ◽  
Ivan García-Orozco
Keyword(s):  
Solid State ◽  
Coordination Polymer ◽  
Elemental Analysis ◽  
Chloroform Solution ◽  
Magnetization Measurements ◽  
One Dimensional ◽  
H Nmr

Bis-[methyl-1-hydroxy-1-cyclopentene-2-dithiocarboxylate-O,S]nickel(II) 1 was prepared starting from methyl 2-hydroxycyclopent-1-encarbodithioate ligand (CPDT) and Ni(II), and catena-[(μ2-4,4′-Bipyril)-bis-(methyl-2-hydroxy-1-cyclopentene-2-dithiocarboxylate-O,S)]nickel(ΙΙ) 2 was prepared in good yields from 1 plus 4,4′-bipyridyl (bpy) by shish-kebab methodology. The structure of 1 was confirmed by FTIR, elemental analysis, 1H NMR, UV–vis in chloroform solution and in solid, XPS, and PXRD. Compound 2 was characterized by FTIR, elemental analysis, UV–vis in chloroform solution, and in solid, XPS, PXRD, ESR, and solid state magnetization measurements. The structure of the polymer was established mostly by PXRD, ESR, and magnetization.

scholarly journals Effect of the coordination of π-acceptor 4-cyanopyridine ligand on the structural and electronic properties of meso-tetra(para-methoxy) and meso-tetra(para-chlorophenyl) porphyrin cobalt(ii) coordination compounds. Application in the catalytic degradation of methylene blue dye

RSC Advances ◽  
2020 ◽  
Vol 10 (12) ◽  
pp. 6900-6918 ◽  
Author(s):  
Mouhieddinne Guergueb ◽  
Soumaya Nasri ◽  
Jihed Brahmi ◽  
Frédérique Loiseau ◽  
Florian Molton ◽  
...  
Keyword(s):  
Methylene Blue ◽  
Cyclic Voltammetry ◽  
Electronic Properties ◽  
Catalytic Oxidation ◽  
Coordination Compounds ◽  
Molecular Structures ◽  
Blue Dye ◽  
Methylene Blue Dye ◽  
H Nmr ◽  
Structural And Electronic Properties

Preparation and UV/vis, IR, MS, 1H NMR, cyclic voltammetry and molecular structures of two new Co(ii) complexes with para-methoxy-phenyl and para-chloro meso-porphyrins and 4-cyanopyridine ligand (1–2). Catalytic oxidation data of MB dye using 1–2.

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