Study of Electronic Structure and Simulation of Molecular Rearrangements of MOCVD Precursors to Predict Their Thermal Stability Upon Evaporation on the Example of Heteroleptic Copper(II) Complexes | Sciact - CRIS-система Института катализа

Study of Electronic Structure and Simulation of Molecular Rearrangements of MOCVD Precursors to Predict Their Thermal Stability Upon Evaporation on the Example of Heteroleptic Copper(II) Complexes Научная публикация

Журнал

Journal of Structural Chemistry
ISSN: 0022-4766 , E-ISSN: 1573-8779

Вых. Данные

Год: 2024, Том: 65, Номер: 5, Страницы: 895-906 Страниц : 12 DOI: 10.1134/S0022476624050044

Ключевые слова

metal diketonates, heteroleptic copper complexes, thermal stability, ligand exchange, electronic structure, MOCVD precursors

Авторы

Kryuchkova N.A. ¹ , Stadnichenko A.I. ² , Korotaev E.V. ¹ , Krisyuk V.V. ¹

Организации

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2	Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

Информация о финансировании (2)

1	Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)	FWUZ-2021-0005 (121031700313-8)
2	Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)	FWUZ-2021-0006 (121031700314-5)

An approach for predicting stability of organometallic precursors during evaporation for chemical vapor deposition is considered on the example of isostructural heteroleptic copper complexes [Cu(acac)(hfac)]2 (1) and [Cu(ki)(hfac)]2 (2). The electron density distribution in binuclear molecules of 1 and 2 is studied by the density functional theory (DFT) and X-ray photoelectron spectroscopy (XPS). It is established that the highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs) of these complexes are characterized by the same composition and structure, their metal–ligand bonds and bridging Cu–O bonds in dimers have close energies, and their donor and central atoms have equal charges. It is shown that the differences between resistances of the studied heteroleptic complexes to the disproportionation upon condensed-phase heating, leading to the formation of homoleptic complexes, are determined by the kinetics of the process. We propose a mechanism of thermally activated ligand-exchange reaction as a series of rearrangements of dimeric complexes in crystals. It is shown from the calculated ΔE and ΔG values that 2 is thermally more stable than 1 due to the presence of an energy barriers it encounters at each stage of the process.

Kryuchkova N.A. , Stadnichenko A.I. , Korotaev E.V. , Krisyuk V.V.
Study of Electronic Structure and Simulation of Molecular Rearrangements of MOCVD Precursors to Predict Their Thermal Stability Upon Evaporation on the Example of Heteroleptic Copper(II) Complexes
Journal of Structural Chemistry. 2024. V.65. N5. P.895-906. DOI: 10.1134/S0022476624050044 WOS Scopus РИНЦ OpenAlex

Крючкова Н.А. , Стадниченко А.И. , Коротаев Е.В. , Крисюк В.В.
Исследование электронной структуры и моделирование молекулярных перегруппировок MOCVD прекурсоров для прогнозирования их термической стабильности при испарении на примере гетеролептических комплексов меди(II)
Журнал структурной химии. 2024. Т.65. №5. 126248 . DOI: 10.26902/JSC_id126248 РИНЦ OpenAlex

Поступила в редакцию:	21 нояб. 2023 г.
Принята к публикации:	10 янв. 2024 г.
Опубликована в печати:	1 мая 2024 г.
Опубликована online:	28 июн. 2024 г.

Web of science:	WOS:001258682200018
Scopus:	2-s2.0-85197457646
РИНЦ:	68379888
OpenAlex:	W4400117655

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