From Isolated Anions to Polymer Structures through Linking with I2: Synthesis, Structure, and Properties of Two Complex Bismuth(III) Iodine Iodides

Shestimerova, T.A.; Yelavik, N.A.; Mironov, A.V.; Kuznetsov, A.N.; Bykov, M.A.; Grigorieva, A.V.; Utochnikova, V.V.; Lepnev, L.S.; Shevelkov, A.V.

Авторы: Shestimerova Tatiana A., Yelavik Natallia A., Mironov Andrei V., Kuznetsov Alexey N., Bykov Mikhail A., Grigorieva Anastasia V., Utochnikova Valentina V., Lepnev Leonid S., Shevelkov Andrei V.
Журнал: Inorganic Chemistry
Том: 57
Номер: 7
Год издания: 2018
Издательство: American Chemical Society
Местоположение издательства: United States
Первая страница: 4077
Последняя страница: 4087
DOI: 10.1021/acs.inorgchem.8b00265
Аннотация: We report synthesis, crystal structures, and optical properties of two new compounds, K18Bi8I42(I2)0.5•14H2O (1) and (NH4)7Bi3I16(I2)0.5•4.5H2O (2), as well as the electronic structure of the latter. They crystallize in tetragonal space group P4/mmm with the unit cell parameters a = 12.974(1), c = 20.821(3) Å for 1 and a = 13.061(3), c = 15.162(7) Å for 2. Though 1 and 2 are not isomorphous, their crystal structures display the same structural organization; namely, the BiI6 octahedra are linked by I2 units to form disordered layers in 1 and perfectly ordered chains in 2. The I–I bond distances in the thus formed I–I–I–I linear links are not uniform; the central bond is only slightly longer than in a stand-alone I2 molecule, whereas the peripheral bonds are significantly shorter than longer bonds typical for various polyiodides, which is confirmed by Raman spectroscopy. The analysis of the electronic structure shows that the atoms forming the I–I–I–I subunits transfer electron density from their occupied 5p orbitals onto their vacant states as well as onto 6s orbitals of bismuth atoms that center the BiI6 octahedra. This leads to low direct band gaps that were found to be 1.57 and 1.27 eV for 1 and 2, respectively, by optical absorption spectroscopy. Luminescent radiative relaxation was observed in the near-IR region with the emission maxima of 1.39 eV and 1.24 eV for 1 and 2, respectively, in good agreement with the band structure, despite the strong quenching propensity of I2 moieties.
Добавил в систему: Шестимерова Татьяна Алексеевна

	ИСТИНА	Войти в систему Регистрация
	ФНКЦ РР
	Главная Поиск Статистика О проекте Помощь

ИСТИНА

ФНКЦ РР

From Isolated Anions to Polymer Structures through Linking with I2: Synthesis, Structure, and Properties of Two Complex Bismuth(III) Iodine Iodidesстатья Исследовательская статья