Superoxide-assisted electrochemical deposition of Mn-aminophenyl porphyrins: Process characteristics and properties of the films

Kuzmin, Sergey M.; Chulovskaya, S. A.; Parfenyuk, V. I.

doi:10.1016/j.electacta.2018.09.127

Cited by 27 publications

(6 citation statements)

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“…Induced electrochemical film deposition implies complication of the diffusion transport of superoxide into the solution bulk by occurrence of a chemical reaction on the electrode surface. According to [29][30][31], the superoxide anion-radical interacts with porphyrin, which results…”

Section: Resultsmentioning

confidence: 99%

“…Significant differences between the parameters of the film formation process at the potentials of -0.9 and -1.25 V allow assuming participation of the porphyrin anion in the film deposition mechanisms [40,41] and apparently formation of adducts of the anionic porphyrin form with molecular oxygen [42] and products of chemical reactions occurring in the course of film deposition induced by the superoxide anion-radical [29][30][31].…”

Section: Resultsmentioning

confidence: 99%

“…The method of electrochemical deposition is characterized by simple implementation and allows obtaining well reproducible films of controlled thickness. Here, film formation is possible in the case of aminophenylporphyrins both as a result of polymerization caused by electrochemical precursor oxidation [19][20][21][22][23][24][25][26][27][28] and as a result of interaction between the porphyrin and the electrochemically synthesized superoxide anion-radical ( ) [29][30][31].…”

Section: Introductionmentioning

confidence: 99%

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Kinetics of Induced Deposition of Films Based on Tetrakis(4-Aminophenyl)Porphyrin

2020

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This work confirms formation of surface films of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (H 2 T(4-NH 2 Ph)P) in dimethylsulfoxide in the potential range of oxygen electroreduction. Kinetics of variation of faradaic currents and of the interface characteristics are studied at the working electrode potentials of +0.5 V (porphyrin electrooxidation), -0.9 V (oxygen electroreduction), and -1.25 V (coreduction of porphyrin and oxygen). It is shown that the working electrode surface is passivated at the potential of +0.5 V and faradaic currents decrease fast. At the potentials of -0.9 and -1.25 V, the working electrode surface passivation is less pronounced. As shown by analysis of electrode impedance spectra, a film is formed on the electrode surface under electroreduction conditions (-0.9 and -1.25 V), as opposed to electrooxidation conditions (+0.5 V). Charge transport through this film can be characterized by modeling the interface impedance. The kinetics of variation of the interface parameters allow estimating the stage mechanism of film formation and restructuring of the formed layer.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Kinetics of Induced Deposition of Films Based on Tetrakis(4-Aminophenyl)Porphyrin

2020

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“…Потенциалы необратимых процессов электровосстановления (Red 1 , Red 2 , Red 3 ) и электроокисления (Ox 1 ) макроцикла мета-замещенного порфирина так же положительнее, чем пара-замещенного. [55] наблюдается большая скорость взаимодействия супероксида с MnClT(4-NH 2 Ph)P, по сравнению с MnClT(3-NH 2 Ph)P. То же самое было показано для амино-замещенных тетрафенилпорфинов-лигандов в других наших работах. [56] На ЦВА растворов порфиринов в ДМСО, насыщенных кислородом, наблюдалось отличие потенциалов пиков окислительно-восстановительных процессов, связанных с порфирином или кислородом, от потенциалов пиков этих же процессов, происходящих в чистом ДМСО без порфирина (для кислорода) или в деаэрированном (без кислорода) растворе порфирина (для порфирина).…”

Section: Electrodeposition and Characterization Of Polyporphyrin Filmsunclassified

Electrodeposition and Characterization of Polyporphyrin Films Based on Mn Complexes of Amino-substituted Tetraphenylporphyrins

Parfenyuk¹,

Tesakova²,

Chulovskaya³

et al. 2019

MHC

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В работе представлены результаты исследования электрохимического осаждения и физико-химических свойств полипорфириновых пленок, осажденных на стеклоуглероде, платине, золоте и ITO-электродах из дихлорметана (ДХМ), этанола и диметилсульфоксида (ДМСО). В качестве прекурсоров использованы хлориды Mn(III) 5,10,15,20-тетракис(3-аминофенил)порфина и Mn(III) 5,10,15,20-тетракис(4-аминофенил)порфина. Показано, что из ДМСО полипорфириновая пленка формируется в области потенциалов электровосстановления кислорода. В ДХМ и этаноле образование пленок на рабочих электродах в процессе электроокисления порфирина-мономера наблюдается в области потенциалов от 0 до +2 В. Процесс электрополимеризации изучен с использованием метода кварцевого микробаланса. Прирост массы пленки MnClT(3-NH 2 Ph)P при осаждении из ДХМ в потенциостатическом режиме в 1,9 раза больше, чем в потенциодинамическом. Поверхность пленок изучена с использованием метода сканирующей электронной микроскопии. Определено количество электронов, участвующих в процессе электрополимеризации. В работе подробно исследованы электрохимические свойства MnClT(3-NH 2 Ph)P и MnClT(4-NH 2 Ph)P в растворах ДМСО и особенности электрохимического осаждения пленок с использованием супероксид анион-радикала. На Pt, ITO и Au электродах происходит формирование полипорфириновой пленки, ассоциированное с пиком электровосстановления кислорода. Наблюдаемые нами изменения на циклических вольтамперограммах растворов порфиринов в ДМСО, насыщенных кислородом, вероятно, указывают на формирование оксокомлексов, в которых металл приобретает устойчивую степень окисления. Материал электрода влияет на амплитуды токов RedОx процессов, величину прироста массы и процессы десорбции осажденного слоя. Скорость взаимодействия O 2 •с MnClT(4-NH 2 Ph)P более высокая, чем с MnClT(3-NH

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“…These are the high charge carrier mobility, p‐channel, n‐channel, and ambipolar charge transport associated with the tunable HOMO and LUMO energy levels, the electron‐donor ability favoring photoinduced electron transfer (PET), the strong light absorption from the ultraviolet to the near‐infrared (IR) region, and the high reactivity of axial positions in the molecule. Metalloporphyrins (MPs) are studied and applied ascatalysts, [ 4–8 ] , chemical probes for ions, ion pairs, volatile organic compounds (VOCs), nitroaromatic compounds, gases, reactive oxygen species, [ 9 ] optical chemosensors, [ 10–16 ] semiconductors, [ 17–21 ] functional dyes for organic solar cells, [ 19,22–24 ] and photodynamic therapy. [ 19,25,26 ] Porphyrin/phthalocyanine derivatives of both the paramagnetic ions of 3 d elements and rare earth element (REE) were widely studied as single‐molecule magnets (SMMs) at the temperatures close to 0 K. [ 27–32 ] The derivatives displaying the Curie–Weiss behavior above the Curie temperature were studied as materials with a magnetocaloric effect (MCE) at the temperature close to room that is far from the temperature of the magnetic phase transition.…”

Section: Introductionmentioning

confidence: 99%

Recent progress in organometallic porphyrin‐based molecular materials for optical sensing, light conversion, and magnetic cooling

Ломова

2021

Applied Organom Chemis

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We present the review of fundamental parameters and properties of metalloporphyrins/phthalocyanines with axial covalent M-O/M-N bonds (M is a metal atom in the oxidation degree more than 2+) for use in the development of the chemistry of molecular materials. The porphyrin complexes covalently bonded along the axial axis are differed by the high oxidation state of a metal atom and related heightened axial reactivity compared with the corresponding derivatives of two charged metal cations, applications of which in both scientific studies and practical areas are most widely reflected in publications. The selection of chemical structures of the 3d, 4d, 5d, and 4f metal derivatives of porphyrins/phthalocyanines and study of their properties promising in the detection of bioactive organic bases, optoelectronics (active components of allsmall molecular organic solar cells), and spintronics (room-temperature magnetocaloric materials) are detailed in the article. The results of the first critical analysis of this topic in the review and the insight into chemical structure effects in the function of MPXs/MPcXs as molecular materials will contribute to further development of their organometallic chemistry.

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Superoxide-assisted electrochemical deposition of Mn-aminophenyl porphyrins: Process characteristics and properties of the films

Cited by 27 publications

References 73 publications

Kinetics of Induced Deposition of Films Based on Tetrakis(4-Aminophenyl)Porphyrin

Kinetics of Induced Deposition of Films Based on Tetrakis(4-Aminophenyl)Porphyrin

Electrodeposition and Characterization of Polyporphyrin Films Based on Mn Complexes of Amino-substituted Tetraphenylporphyrins

Recent progress in organometallic porphyrin‐based molecular materials for optical sensing, light conversion, and magnetic cooling

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