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Imidazoporphyrins as supramolecular tectons: synthesis and self-assembling of zinc 2-(4-pyridyl)-1H-imidazo[4,5-b]porphyrinateстатья Исследовательская статья
Статья опубликована в высокорейтинговом журнале
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: 24 января 2020 г.
- Авторы: Birin Kirill P., Inna Abdulaeva, Sinelshchikova Anna A., Grigoriev Mikhail S., Lyssenko Konstantin A., Gorbunova Yulia G., Tsivadze Aslan Yu, Bessmertnykh-Lemeune Alla
- Журнал: CrystEngComm
- Том: 21
- Год издания: 2019
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 1488
- Последняя страница: 1498
- DOI: 10.1039/c8ce01992d
- Аннотация: 5,10,15,20-Tetramesityl-2-(4-pyridyl)-1H-imidazo[4,5-b]porphyrin (PyPor) bearing a pyridine donor site connected to the tetrapyrrolic macrocycle by a rigid imidazole linker was prepared in high yield by the condensation of the corresponding 2,3-dioxochlorin and 4-formylpyridine in the presence of ammonium acetate. After the insertion of a metal ion capable of metal–ligand axial coordination, namely Zn(II), this compound afforded self-complementary porphyrin PyPorZn which was suitable for self-assembly. In the crystals, this complex exists as a zigzag coordination polymer formed through the axial coordination of the pyridine nitrogen atom to the zinc ion of the neighbouring porphyrin molecule. The Zn atoms adopt a distorted tetragonal pyramidal environment and the pyridine rings significantly deviate from the orthogonal orientation to the mean N4 plane of the adjacent macrocycle (the Cpara–NPy–Zn angle is equal to 148°). This distortion was analysed by using DFT calculations of a zinc 5,10,15,20-tetraphenylporphyrinate–pyridine complex (TPPZn–Py). The energy and the geometry of TPPZn–Py were calculated by varying the tilt of the pyridine ligand. The change of the Cpara–NPy–Zn angle from 180° to 150° induces a small increase (within 1.5 kcal mol−1) of the total energy of the complex. Such a small increase can be easily compensated by the intermolecular CH⋯H and CH⋯π interactions in the crystals. The self-assembly of PyPorZn in non-coordinating solvents was also investigated by NMR and UV-vis spectroscopy. In contrast to the nickel complex PyPorNi, the zinc complex exists in 10−4 M solution in toluene and chloroform as a mixture of short linear oligomers. These oligomers dissociate affording monomer species upon heating, dilution or addition of a substituting ligand.
- Добавил в систему: Бирин Кирилл Петрович