Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu4/M4 Architectures | Sciact - CRIS-система Института катализа

Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu4/M4 Architectures Научная публикация

Журнал

Crystal Growth and Design
ISSN: 1528-7483 , E-ISSN: 1528-7505

Вых. Данные

Год: 2022, Том: 22, Страницы: 2146−2157 Страниц : 12 DOI: 10.1021/acs.cgd.1c01225

Ключевые слова

Architectural design; Positive ions; Product design; Silicon compounds; Single crystals; Synchrotron radiation

Авторы

Bilyachenko Alexey N. ^1,2 , Astakhov Grigorii S. ^1,2 , Kulakova Alena N. ^1,2 , Korlyukov Alexander A. ^2,3 , Zubavichus Yan V. ⁴ , Dorovatovskii Pavel V. ⁵ , Shul’pina Lidia S. ² , Shubina Elena S. ² , Ikonnikov Nikolay S. ² , Kirillova Marina V. ⁶ , Zueva Anna Y. ¹ , Kirillov Alexander M. ⁶ , Shul’pin Georgiy B. ^7,8

Организации

1	Peoples’ Friendship University of Russia, 117198 Moscow, Russia
2	A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991 Moscow, Russia
3	Pirogov Russian National Research Medical University, Moscow 117997, Russia
4	Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis SB RAS, Koltsovo 630559, Russia
5	National Research Center “Kurchatov Institute”, 123182 Moscow, Russia
6	Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal
7	N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow 119991, Russia
8	Plekhanov Russian University of Economics, Moscow 117997, Russia

Информация о финансировании (8)

1	Российский фонд фундаментальных исследований	20-03-00542
2	Foundation for Science and Technology	PTDC/QUI-QIN/3898/2020
3	Foundation for Science and Technology	CEECIND/03708/2017
4	Foundation for Science and Technology	LISBOA-01-0145-FEDER-029697
5	Foundation for Science and Technology	UIDB/00100/2020
6	Foundation for Science and Technology	LA/P/0056/2020
7	Министерство образования и науки Российской Федерации
8	Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)

Within the sweeping research on the design of new coordination polymers and related metal–organic architectures, the use of silsesquioxane derivatives as important organosilicon building blocks has been poorly explored, despite a number of unique structural and functional characteristics of the resulting products. The present study thus describes an extended series (eight examples) of heterometallic Cu4Cs4 and Cu4Rb4 coordination polymers with the common formula [(PhSiO1.5)12(CuO)4(AO0.5)4(Solv)x]n·nSolv (A is Cs or Rb; Solv refers to ligands and/or solvate molecules including H2O, EtOH, BuOH, DMF, and DMSO in various combinations), which are based on cagelike coppersilsesquioxanes as nontrivial secondary building units. The concept of supramolecular design was implemented in a straightforward way by the assembly of coppersilsesquioxane cages using large and coordination-versatile cesium or rubidium cations. The structures of all products were established by single-crystal X-ray diffraction studies mainly using synchrotron radiation. The resulting Cu4Cs4- and Cu4Rb4-silsesquioxanes exhibit an extracage location of the alkali-metal cations, which enables the interconnectivity of neighboring cages into 1D, 2D, or 3D coordination polymer architectures. The unique feature of such architectures is a realization of metallocene Cs···π (Rb···π) joints, providing tightly connected nonporous coordination polymers. A topological classification of cages and coordination polymer networks was performed. Some of the obtained compounds also represent the first examples of Rb-containing silsesquioxanes. The selected products were also tested as homogeneous catalysts in the oxidation and hydrocarboxylation of C5–C8 cycloalkanes. This study extends the structural types of heterometallic silsesquioxane cages that can be efficiently applied to the design of functional coordination polymers.

Bilyachenko A.N. , Astakhov G.S. , Kulakova A.N. , Korlyukov A.A. , Zubavichus Y.V. , Dorovatovskii P.V. , Shul’pina L.S. , Shubina E.S. , Ikonnikov N.S. , Kirillova M.V. , Zueva A.Y. , Kirillov A.M. , Shul’pin G.B.
Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu4/M4 Architectures
Crystal Growth and Design. 2022. V.22. P.2146−2157. DOI: 10.1021/acs.cgd.1c01225 WOS Scopus РИНЦ CAPlusCA OpenAlex СКИФ ID

Поступила в редакцию:	20 окт. 2021 г.
Принята к публикации:	14 февр. 2022 г.
Опубликована online:	23 февр. 2022 г.
Опубликована в печати:	6 апр. 2022 г.

Web of science:	WOS:000784812500016
Scopus:	2-s2.0-85125907570
РИНЦ:	48153570
Chemical Abstracts:	2022:456226
Chemical Abstracts (print):	178:132823
OpenAlex:	W4221094957
СКИФ ID:	518

БД	Цитирований
Scopus	15
РИНЦ	11
Web of science	15
OpenAlex	15