Oxoammonium enabled secondary doping of hole transporting material PEDOT:PSS for high-performance organic solar cells

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate(PEDOT:PSS)is one of the most widely used hole transporting materials in organic solar cells(OSCs).Multiple strategies have been adopted to improve the conductivity of PEDOT:PSS,however,effective strategy that can optimize the conductivity,work function,and surface energy simultaneously to reach a better energy alignment and interface contact is rare.Here,we demonstrate that oxoammonium salts(TEMPO^+X^-)with different counterions can act as facile and novel dopants to realize secondary doping of PEDOT:PSS.The effective charge transfer process achieved between TEMPO^+X^-and PEDOT:PSS results in enhanced carrier density and improved conductivity of PEDOT:PSS.Moreover,different counterions of TEMPO^+X^-can tune the work function and surface energy of PEDOT:PSS,enabling improved device performances.The resulting device with PM6:Y6 as the active layer shows a high power conversion efficiency(PCE)over 16%.Moreover,this doping strategy can also be applied to other conjugated polymers such as poly(3-hexylthiophene).This work provides a promising strategy to tune the properties of conjugated polymers through doping,thus effectively boosting the performance of organic solar cells.

Oxyfunctionalization of ketones bearing α-methylene group with piperidine oxoammonium salt.Synthesis of α-diketones from monoketones

A facile method for the title transformation is described. The reaction of 2,2,6,6-tetramethyl-4-methoxypiperidine oxoammonium chloride (1b) and ketones bearing a-methylene group in acetonitrile proceeded smoothly to give the a-oxyfunctionalized coupling products (6a-h). These coupling products decomposed upon heating in acidic medium to produce a-diketones (7a-h) in good to excellent yields.

Kinetic studies on the single electron transfer reaction between 2, 2, 6, 6-tetramethylpiperidine oxoammonium ions and phenothiazines: the application of Marcus theory

Electron transfer reactions take place readily between 2, 2, 6, 6-tetramethylpiperidine oxoammonium ions (1a, 1b) and phenothiazines (2a—2g), giving corresponding nitroxides (3a, 3b) and phenothiazine radical cations (4a—4g). The rate constants for the electron self-exchange reactions between 1 and 3, as well as between 2 and 4, are determined by EPR and ~1H NMR line-broadening effect in acetonitrile. By application of the Marcus theory, the kinetics of the cross-exchange reactions between 1 and 2 is studied.

一种快速无污染高收率的氧化法制备醛和酮

采用5%次氯酸钠水溶液为氧化剂,Tempo为催化剂,由3-羟基环庚酮缩乙二醇制备1,3-环庚酮,收率高,成本低,无三废,可扩大生产。

Decarboxylative Alkylation of β-Keto Acids with Isochromans under Oxidative Conditions

An unprecedented decarboxylative alkylation reaction of fl-keto acids with isochromans has been developed under oxidative conditions. A range of β-keto acids smoothly undergo decarboxylative alkylation with isochromans in the presence of 2,2,6,6-tetramethylpiperdine-1-oxoammonium hexafluorophosphate to give structurally diverse 1-acylmethylisochromans in moderate to excellent yields with extremely high regioselectivity.

Electron transfer reactions of piperidine aminoxyl radicals

This review article summarizes the electron transfer reactions of piperidine aminoxyl radicals. Electrochemical studies revealed the single electron transfer nature of piperidine aminoxyl radicals. In solution, piperidine aminoxyl radicals serve as single electron transfer oxidation reagent to react with various biologically interesting molecules such as glutathione, cysteine, ascorbic acid, and amines. The reaction product distribution, reaction kinetics, intermediates, and the reaction features in biological mimic environments including micelles and cyclodextrins were investigated. Oxoammonium salts, the one-electron transfer oxidation products of piperidine aminoxyl radicals, are agents of organic synthesis to selectively generate ketones or di-ketones from alcohols or ketones bearing α-methylene group under mild conditions. The new reactions of oxoammonium salts with aromatic amines, phenols, heterocycles including phenothiazines, papaverine, and bilirubin are also illustrated.

Total Synthesis of Laurane and Guaiane Sesquiterpenoids via Oxidative Nazarov Reaction

As one of the most common structural motifs in natural products,cyclopentenones usually can be fabricated by Nazarov cyclization using divinyl ketones or functionalized tertiary divinyl carbinols(TDCs)as substrates.However,straightforward method for transforming unfunctionalized TDCs to their corresponding cyclopentenones is currently lacking.Herein,we wish to report the total syntheses of four structurally distinct terpenoids,namely laurane-type marine sesquiterpenoids isolaurene,debromoaplysin and aplysin,and guaiane sesquiterpenoid guaiadienone A,all using a novel synthetic method,named oxidative Nazarov cyclization,as the key step.This work demonstrated our robust method is suitable for synthesizing various highly substituted cyclopentenones.