The synthesis of alkoxycarbonyl-substituted bisaziridines with the two aziridine units connected by conjugated p-phenylene, partly conjugated 1,1'-biphenyl-4,4'-diyl, and nonconjugated 4,4'-methylenediphenyl linkers was developed. The reaction of azomethine ylides derived from the bisaziridines with fullerene C(60) was optimized and used for the stereoselective preparation of both the monoadducts (C(60)-linker-aziridine dicarboxylate), and the dumbbell bisadducts (C(60)-linker-C(60)). The reasons for the observed selectivity of the azomethine ylide formation and cycloaddition were theoretically studied at the DFT B3LYP/6-31G(d) level or at the ONIOM B3LYP/6-31G(d):B3LYP/STO-3G level for fullerene-containing molecules.
The nickel salen‐type redox polymers represent an interesting class of organometallic polymers frequently used in hybrid supercapacitor electrodes as thin films and carbon material composites. However, the suitability of these compounds for application as electrode materials for rechargeable batteries has not yet been tested. In this study, redox processes in monocomponent electrodes based on a series of nickel salen‐type redox polymers are investigated in 1 m LiPF6 in 1:1 ethylene carbonate (EC)/diethyl carbonate (DEC) electrolyte in a Li‐ion battery. The oxidation potentials for polymer complexes of nickel exceed 3.5 V versus Li/Li+, which enhances specific energy. It is found that introduction of a proper substituent in the phenyl ring of the ligand allows to fabricate additive‐free electrodes which demonstrate high charge/discharge rate performance with the capacity on discharge at 10C being up to 73% of the capacity obtained at discharge at 1C, which corresponds to maximum power of 2.6 kW kg−1.
The quantum-chemical calculations of the thermal ring opening of 1-methyl-2,3-diphenyl-and 1,2,3-triphenylaziridine with formation of the corresponding azomethine ylides of S-, U-, and W-type as well as their cycloaddition to dimethyl acetylenedicarboxylate (DMAD) and dimethyl 2,3-dicyanobut-2-enedioate, were performed at the DFT B3LYP/6-31G(d) level of theory with the PCM solvation model. The calculations are in complete accordance with experimental results and explain the switch from the concerted to the non-concerted pathway depending on substituents in the dipolarophile and the ylide. It was found that strong electron-withdrawing substituents in dipolarophiles, such as in dialkyl dicyanobutenedioates, significantly reduce the barrier for the formation of zwitterionic intermediates in the reaction of azomethine ylides with such dipoles. This can render the stepwise cycloaddition competitive with the concerted one. However, the concertedness of the cycloaddition even to dipolarophiles with several electron-withdrawing substituents is governed by a fine balance of electronic and steric effects in both ylide and dipolarophile counterparts. The hypothesis that introduction of substituents in the azomethine ylide that destabilize the positive charge in a corresponding zwitterion will favor the concerted cycloaddition even with dialkyl dicyanobutenedioates was tested theoretically and experimentally.
A new approach to porphyrinofullerene donor-acceptor dyads, based on consecutive 1,3-dipolar cycloaddition of azomethine ylides, generated from bis-aziridinedicarboxylate, to C60 and to porphyrin with a maleimidophenyl substituent, was developed. A synthesis of the axially symmetric porphyrin-fullerene-C60 ensemble 5 with a novel rigid pyrrolo[3,4-c]pyrrolic linker was realized. Theoretical, electrochemical, and spectroscopic studies of compound 5 showed that it is capable of forming a charge-separated state.
Electroactive and conductive polymers based on transition metal complexes with salen‐type ligands are of interest as potential materials for energy storage and solar energy conversion. The easily tunable structure of monomers allows to modify polymer properties by changing either the central metal atom or the ligand substituents. Herein we report the photoelectrocatalytic activity of [MII(L)]n complexes, where M is Ni, Cu or Pd, and L is a tetradentate N,N,O,O salen‐type ligand, in the reduction of molecular oxygen to hydrogen peroxide in water solutions on polymer‐coated ITO electrodes. The photocathodic current at 0 V vs. Ag/AgCl is pH‐dependent, reaching maximum at pH 1 and dropping almost to zero at pH 12. Hydrogen peroxide production is almost quantitative (97 % efficiency measured in 1‐compartment cell). Maximal photocurrent and H2O2 concentrations achieved comprise 23 μA/cm2 and 1.3×10−3 M respectively.
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