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Effect of metalation-demetalation reactions on the assembly and properties of 2D supramolecular arrays of tetrapyridylporphyrin and its Zn(II)-complexстатья
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 5 июня 2017 г.
- Авторы: Ermakova E.V., Meshkov I.N., Enakieva Yu Yu, Zvyagina A.I., Ezhov A.A., Mikhaylov A.A., Gorbunova Yu G., Chernyshev V.V., Kalinina M.A., Arslanov V.V.
- Журнал: Surface Science
- Том: 660
- Год издания: 2017
- Издательство: Elsevier BV
- Местоположение издательства: Netherlands
- Первая страница: 39
- Последняя страница: 46
- DOI: 10.1016/j.susc.2017.02.007
- Аннотация: We suggested a new approach to the assembly of highly ordered 2D-coordination networks of tetrapyridyl porphyrins (TPyP) in Langmuir monolayers of the metal-free ligand as a primary building unit. For this type of planar systems, the formation of perfectly structured 2D multiporphyrin arrays with face-on arrangement of macrocycles is assisted by the interactions of metal ions with porphyrin ring as well as by those with peripheral pyridyl groups. By using a combination of in-situ optical spectroscopy methods, we found that the metalation of metal-free porphyrin in the monolayers is critically important for the formation of networked supramolecular assemblies. When compared with similar reaction in solution, the incorporation of zinc ions into the porphyrin ring in monolayers occurs at higher concentration of the metal salt and proceeds comparatively slowly. Zinc ions boost the fluorescence of TPyP in organic solvent, whereas their presence in the subphase under the monolayer of TPyP results in fluorescence quenching. The observed effects are the consequence of structure-dependent metalation/demetalation processes, which occurs in these porphyrin-based systems. Oxygen, which is naturally present in the solvent as well as in the subphase under standard experimental conditions, also assists the decrease of photoluminescence. Metalation/demetalation processes play a key role at every step of fabrication of surface-anchored metal-organic frameworks starting from the preparation of spreading solution and until the formation of ion-coordinated monolayer at the air/water interface. Our approach makes it possible to obtain uniformly smooth ultrathin films, which thickness measured by AFM is consistent with that determined by X-ray reflectometry for similar 2D network. The obtained results provide a basis for better understanding of formation and ordering of ultimately thin metal organic coordinated structures at interfaces.
- Добавил в систему: Ежов Александр Анатольевич