Reduction potentials of <i>para</i>‐substituted nitrobenzenes—an infrared, nuclear magnetic resonance, and density functional theory study

Kuhn, Annemarie; Eschwege, Karel G. von; Conradie, Jeanet

doi:10.1002/poc.1868

Cited by 90 publications

(65 citation statements)

References 59 publications

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“…These data may be used for answering the question: Does the electron acceptance of the nitro group (i.e., electroreduction) in various chemical species follow the trend in EAP values estimated by using of the cSAR concept? Table 1 presents the half-wave potentials (E 1/2 ) for p-nitrobenzene-X derivatives measured in dimethylformamide with tetrammonium perchlorate as a supporting electrolyte [16] as well as the formal reduction potentials (E 0 ) measured in dry acetonitrile with tetra-n-butylammonium hexafluorophosphate as supporting electrolyte [17], substituent X constants (r p , r p ? ) and cSAR values.…”

Section: Csar(no 2 ) As a Numerical Characteristic Of The Eap Of The mentioning

confidence: 99%

“…The variability of its EAP is nicely illustrated by experimental measurements of the polarographic half-wave potentials, E 1/2 , of the reversible one-electron reduction of substituted nitrobenzene derivatives carried out in aprotic solvents to avoid subsequent kinetics [16], as well as by their formal reduction potentials [17], E 0 . In this way, the obtained E 1/2 as well as E 0 values are thermodynamic properties and may serve as reliable descriptors of relations between structure and energetic characteristics of the molecules.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical study of electron-attracting ability of the nitro group: classical and reverse substituent effects

Stasyuk

Szatyłowicz

Guerra³

et al. 2015

Struct Chem

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This study presents a quantum chemistry modeling of the substituent effect. For this purpose, a uniform approach-the model termed as ''charge of substituent active region'' (cSAR, defined as a sum of atomic charges at the substituent and the ipso carbon atom)-has been used. Its reliability has been confirmed by a quantitative description of the electron-attracting ability of the nitro group, and finally, the reverse substituent effect, showing the influence of reaction site (Y) on the properties of substituent (X), has been introduced and documented. The cSAR model has been applied to para-substituted nitrobenzene derivatives in which the nitro group acts either as a reaction site (classical substituent effect, with X = NO 2 , CN, CHO, COOMe, COMe, CF 3 , Cl, H, Me, OMe, NH 2 and NHMe) or as a substituent (reverse substituent effect, with Y = NH -, NH 2 , H and NH 3 ? ).Calculation was performed using BLYP functional with DFT-D3 correction and TZ2P basis set. Application of different assessments of atomic charges (Voronoi, Hirshfeld, Bader, Weinhold and Mulliken) leads to good correlation between calculated cSAR values. Graphical Abstract Electron-attracting ability of the nitro group depends dramatically on the electron-donating properties of the reaction site

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Section: Csar(no 2 ) As a Numerical Characteristic Of The Eap Of The mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical study of electron-attracting ability of the nitro group: classical and reverse substituent effects

Stasyuk

Szatyłowicz

Guerra³

et al. 2015

Struct Chem

View full text Add to dashboard Cite

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“…[ 30,35,36 ] For molecules closely related in structure, reduction potentials are linearly related to the LUMO energies. [ 43 ] Using density functional theory calculations, Andrzejak et al [ 44 ] have demonstrated that altering the aromatic system from PMDA to NTCDA and PTCDA lowers the LUMO energy and thus the increased average discharge voltage from PMDA-based to NTCDA-based and PTCDA-based PIs is reasonable. We expect a substitution with much stronger electronwithdrawing groups, such as cyano and bromine, will enable further elevation of the redox potential of PIs.…”

mentioning

confidence: 98%

Tailored Aromatic Carbonyl Derivative Polyimides for High‐Power and Long‐Cycle Sodium‐Organic Batteries

Wang

Yuan

et al. 2013

Advanced Energy Materials

342

272

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Pressing concerns about limited reserve and distribution of lithium resources have led to an increasing interest in replacing lithium-ion batteries (LIBs) from a viewpoint of sustainability. [1][2][3][4][5][6] In response, sodium-ion batteries (NIBs) are an attractive alternative because sodium resources are practically inexhaustible and ubiquitous, for example, the cost of Na 2 CO 3 is only 3% of the cost of Li 2 CO 3 . [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] However, as only a very limited number of materials are reported to be viable up to now, [ 23,24 ] the performance of the NIBs is still terribly plagued by low specifi c capacity, poor rate capability, and short cycle life. On the other hand, the commonly used electrode materials in LIBs and NIBs are rely heavily on depletable metal-based inorganic compounds prepared from limited mineral resources, thus giving rise to the problem of cost and environmental concerns. Therefore, there is an urgent need to prepare future electrode materials, shifting from inorganic to organic materials that are more abundant, from renewable resources with minimum energy consumption. They are also required to have high power density and long cycling stability.Organic materials, and in particular organic carbonyl compounds, are considered to be promising electrode materials due to their numerous advantages, including lightweight, redox stability, multi-electron reactions, and availability from easily accessible natural sources. [25][26][27][28][29][30][31][32][33][34][35][36][37] Furthermore, organic synthesis techniques and quantum chemical considerations enable the performance of batteries to be tuned on the molecular level, that is, to tailor secondary batteries. [ 25 ] Due to the less rigid structure compared to inorganic counterparts, organic compounds are structurally more fl exible and thus could facilitate the higher mobility of large-sized sodium ions, which is vital to the operation of NIBs. [ 38 ] Furthermore, no strongly oxidizing substance would be generated during the charge/discharge process of organic materials, which could at least alleviate the daunting safety problem of the transition metal oxide (TMOs) cathode. [ 29 ] In this context, very recently, organic carbonyl compounds, such as sodium terephthalate and its derivatives, have been developed as promising organic anodes for NIBs. [39][40][41] However, no corresponding organic compounds or aromatic carbonyl derivatives containing dianhydride as cathode materials for NIBs have been successfully developed until now because the direct implementation of organic molecules in battery systems is diffi cult due to the serious dissolution in electrolyte. [ 29,35,36 ] In response, one very promising strategy is to construct dianhydride-based polymer materials to make a stable and fl exible framework, which could restrain the unwanted dissolution in the electrolyte and achieve fast kinetic properties. [29][30][31][32] Based on the structural characteristics of dianhydride, it is a promising altern...

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“…Next, photoredox catalysis of I was investigated. Since the redox potential of the photo‐reduced I by two electrons (−1.25 V vs. NHE in acetonitrile) is more negative than those of oxygen (−0.65 V vs. NHE in acetonitrile)12 and nitrobenzene and its substituted ones (varying from −1.2 to −0.8 V vs. NHE in acetonitrile),13 the reduction of oxygen and various nitroarenes is thermodynamically possible in the present photoredox system. As expected, the photo‐reduced I was readily reoxidized by exposure to air, and the color of the solution changed from dark blue to pale yellow, indicating that electron transfer from the photo‐reduced I to oxygen proceeds.…”

Section: Photocatalytic One‐pot Synthesis Of N‐(4‐methoxybenzylidene)mentioning

confidence: 92%

Identification of Structural Features of 2‐Alkylidene‐1,3‐Dicarbonyl Derivatives that Induce Inhibition and/or Activation of Histone Acetyltransferases KAT3B/p300 and KAT2B/PCAF

et al. 2014

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Dysregulation of the activity of lysine acetyltransferases (KATs) is related to a variety of diseases and/or pathological cellular states; however, their role remains unclear. Therefore, the development of selective modulators of these enzymes is of paramount importance, because these molecules could be invaluable tools for assessing the importance of KATs in several pathologies. We recently found that diethyl pentadecylidenemalonate (SPV106) possesses a previously unobserved inhibitor/activator activity profile against protein acetyltransferases. Herein, we report that manipulation of the carbonyl functions of a series of analogues of SPV106 yielded different activity profiles against KAT2B and KAT3B (pure KAT2B activator, pan-inhibitor, or mixed KAT2B activator/KAT3B inhibitor). Among the novel compounds, a few derivatives may be useful chemical tools for studying the mechanism of lysine acetylation and its implications in physiological and/or pathological processes.

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Reduction potentials of para‐substituted nitrobenzenes—an infrared, nuclear magnetic resonance, and density functional theory study

Cited by 90 publications

References 59 publications

Theoretical study of electron-attracting ability of the nitro group: classical and reverse substituent effects

Theoretical study of electron-attracting ability of the nitro group: classical and reverse substituent effects

Tailored Aromatic Carbonyl Derivative Polyimides for High‐Power and Long‐Cycle Sodium‐Organic Batteries

Identification of Structural Features of 2‐Alkylidene‐1,3‐Dicarbonyl Derivatives that Induce Inhibition and/or Activation of Histone Acetyltransferases KAT3B/p300 and KAT2B/PCAF

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