Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu4/M4 Architectures | Sciact - CRIS-system of Boreskov Institute of Catalysis

Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu4/M4 Architectures Full article

Journal

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

Output data

Year: 2022, Volume: 22, Pages: 2146−2157 Pages count : 12 DOI: 10.1021/acs.cgd.1c01225

Tags

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

Authors

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

Affiliations

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

Funding (8)

1	Russian Foundation for Basic Research	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	The Ministry of Education and Science of the Russian Federation
8	Ministry of Science and Higher Education of the Russian Federation

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 ANCAN OpenAlex publication_identifier_short.sciact_skif_identifier_type

Submitted:	Oct 20, 2021
Accepted:	Feb 14, 2022
Published online:	Feb 23, 2022
Published print:	Apr 6, 2022

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

DB	Citing
Scopus	16
Elibrary	11
Web of science	16
OpenAlex	15