chemicallytechFine Chemical TechnologiesТонкие химические технологии2410-65932686-7575MIREA – Russian Technological University (RTU MIREA).10.32362/2410-6593-2018-13-2-21-30chemicallytech-138Research ArticleCHEMISTRY AND TECHNOLOGY OF MEDICINAL COMPOUNDS AND BIOLOGICALLY ACTIVE SUBSTANCESХИМИЯ И ТЕХНОЛОГИЯ ЛЕКАРСТВЕННЫХ ПРЕПАРАТОВ И БИОЛОГИЧЕСКИ АКТИВНЫХ СОЕДИНЕНИЙSYNTHESIS AND PROPERTIES COMPARISON OF MESO-ARYLPORPHYRINS METAL COMPLEXES AS POTENTIAL DYES FOR SOLAR CELLSСИНТЕЗ И СРАВНЕНИЕ СВОЙСТВ МЕТАЛЛОКОМПЛЕКСОВ МЕЗО-АРИЛЗАМЕЩЕННЫХ ПОРФИРИНОВ КАК ПОТЕНЦИАЛЬНЫХ КРАСИТЕЛЕЙ ДЛЯ СОЛНЕЧНЫХ ЯЧЕЕКЕжовА. В.EzhovA. V.

аспирант кафедры химии и технологии биологически активных соединений, медицинской и органической химии им. Н.А. Преображенского

119571, Россия, Москва, пр-т Вернадского, д. 86

Postgraduate Student, N.A. Preobrazhenkiy Chair of Chemistry and Technology of Biologically Active Compounds, Medical and Organic Chemistry,

86, Vernadskogo Pr., Moscow 119571, Russia

artem.ejov@gmail.comВяльбаФ. Ю.VyalbaF. Yu.

студент 5 курса кафедры химии и технологии биологически активных соединений, медицинской и органической химии им. Н.А. Преображенского

119571, Россия, Москва, пр-т Вернадского, д. 86

Student, N.A. Preobrazhenkiy Chair of Chemistry and Technology of Biologically Active Compounds, Medical and Organic Chemistry

86, Vernadskogo Pr., Moscow 119571, Russia

noemail@neicon.ruЖдановаК. А.ZhdanovaK. A.

кандидат химических наук, ассистент кафедры химии и технологии биологически активных соединений, медицинской и органической химии им. Н.А. Преображенского

119571, Россия, Москва, пр-т Вернадского, д. 86

Ph.D. (Chemistry), Assistant Professor, N.A. Preobrazhenkiy Chair of Chemistry and Technology of Biologically Active Compounds, Medical and Organic Chemistry,

-86, Vernadskogo Pr., Moscow 119571, Russia

noemail@neicon.ruМироновА. Ф.MironovA. F.

доктор химических наук, профессор кафедры химии и технологии биологически активных соединений, медицинской и органической химии им. Н.А. Преображенского

119571, Россия, Москва, пр-т Вернадского, д. 86

D.Sc. (Chemistry), Professor, N.A. Preobrazhenkiy Chair of Chemistry and Technology of Biologically Active Compounds, Medical and Organic Chemistry

86, Vernadskogo Pr., Moscow 119571, Russia

noemail@neicon.ruЖижинК. Ю.ZhizhinK. Yu.

доктор химических наук, член-корр. РАН, зам. директора

119991, Россия, Москва, Ленинский пр-т., д. 31

профессор кафедры неорганической химии им. А.Н. Реформатского

119571, Россия, Москва, пр-т Вернадского, д. 86

D.Sc. (Chemistry), Corresponding Member of the Russian Academy of Sciences, Deputy Director of N.S. Kurnakov

31, Leninsky Pr., Moscow 119991, Russia

Professor, A.N. Reformatskiy Chair of Inorganic Chemistry

86, Vernadskogo Pr., Moscow 119571, Russia

noemail@neicon.ruБрагинаН. А.BraginaN. A.

кандидат химических наук, доцент кафедры химии и технологии биологически активных соединений, медицинской и органической химии им. Н.А. Преображенского

119571, Россия, Москва, пр-т Вернадского, д. 86

Ph.D. (Chemistry), Associate Professor, N.A. Preobrazhenkiy Chair of Chemistry and Technology of Biologically Active Compounds, Medical and Organic Chemistry

86, Vernadskogo Pr., Moscow 119571, Russia

noemail@neicon.ruМосковский технологический университет (Институт тонких химических технологий им. М.В. Ломоносова)РоссияMoscow Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)Russian FederationМосковский технологический университет (Институт тонких химических технологий им. М.В. Ломоносова); Институт общей и неорганической химии им. Н.С. Курнакова РАНРоссияMoscow Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies); N.S. Kurnakov Institute of General and Inorganic ChemistryRussian Federation2018280420181322130Copyright © Ezhov A.V., Vyalba F.Y., Zhdanova K.A., Mironov A.F., Zhizhin K.Y., Bragina N.A., 20182018Ежов А.В., Вяльба Ф.Ю., Жданова К.А., Миронов А.Ф., Жижин К.Ю., Брагина Н.А.Ezhov A.V., Vyalba F.Y., Zhdanova K.A., Mironov A.F., Zhizhin K.Y., Bragina N.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.finechem-mirea.ru/jour/article/view/138

This work is dedicated to the synthesis of porphyrin metal complexes for creation of dyesensitized solar cells (DSSC). Three different dyes were synthesized - zinc complexes of porphyrins containing alkoxyl substituents: with symmetric structure (Zn-P1), as well as asymmetric (type A3B) with the introduction of a donor (Zn-P2) or an acceptor (Zn-P3) substituents via the 1,3,5-triazine fragment. The spectral characteristics of the synthesized substances are compared. For all the obtained dyes, geometry optimization and visualization of the electron density distribution were carried out using computational methods based on the density functional theory (DFT). The location of the frontier unbound molecular orbitals is more optimal when an acceptor substituent containing anchor groups is introduced via the triazine moiety. However, the use of ligands containing an anchor group simplifies the synthesis of the dye and opens up more possibilities for varying both the ligand and the introduced donor substituents. As a result, it was concluded that the spatial distribution of the dye, when applied to the electrode and, consequently, the number of its molecules per unit area of the semiconductor, can have the greatest effect on the efficiency of a cell using t he described compounds.

Разработаны подходы к синтезу новых мезо-арилпорфиринов с высшими алкоксильными заместителями - потенциальных красителей для фотовольтаики. Получены три различных типа структур порфиринов: симметричный тетраарилзамещенный порфирин (P1), несимметричные (типа А3В) с введением донорных (P2) или акцепторных заместителей через 1,3,5-триазиновый фрагмент (P3), а также их цинковые металлокомплексы (Zn-P1, Zn-P2, Zn-P3, соответственно). Проведено сравнение спектральных характеристик синтезированных веществ. Для полученных красителей проведена оптимизация геометрии и визуализация распределения электронной плотности с помощью расчетных методов, основанных на теории функционала плотности (DFT). Установлено, что более оптимальным расположением граничных вакантных молекулярных орбиталей обладает соединение Zn-P3, содержащее якорные карбоксильные группы. В результате исследования показано, что наибольшее влияние на эффективность ячеек с использованием описанных соединений оказывает пространственное расположение красителя при нанесении на электрод и, как следствие, количество его молекул на единицу площади полупроводника.

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The authors declare that there are no conflicts of interest present.