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Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu4/M4 Architecturesстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Bilyachenko Alexey N., Astakhov Grigorii S., Kulakova Alena N., Korlyukov Alexander A., Zubavichus Yan V., Dorovatovskii Pavel V., Shul’pina Lidia S., Shubina Elena S., Ikonnikov Nikolay S., Kirillova Marina V., Zueva Anna Y., Kirillov Alexander M., Shul’pin Georgiy B.
- Журнал: Crystal Growth and Design
- Том: 22
- Номер: 4
- Год издания: 2022
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 2146
- Последняя страница: 2157
- DOI: 10.1021/acs.cgd.1c01225
- Аннотация: Within the sweeping research on the design of newcoordination polymers and related metal−organic architectures,the use of silsesquioxane derivatives as important organosiliconbuilding blocks has been poorly explored, despite a number ofunique structural and functional characteristics of the resultingproducts. The present study thus describes an extended series(eight examples) of heterometallic Cu4 Cs4 and Cu 4Rb4 coordina-tion polymers with the common formula [(PhSiO 1.5 )12 (CuO)4-(AO0.5) 4(Solv)x]n·nSolv (A is Cs or Rb; Solv refers to ligands and/or solvate molecules including H 2O, EtOH, BuOH, DMF, andDMSO in various combinations), which are based on cagelikecoppersilsesquioxanes as nontrivial secondary building units. Theconcept of supramolecular design was implemented in a straightforward way by the assembly of coppersilsesquioxane cages usinglarge and coordination-versatile cesium or rubidium cations. The structures of all products were established by single-crystal X-raydiffraction studies mainly using synchrotron radiation. The resulting Cu 4Cs4 - and Cu 4Rb4 -silsesquioxanes exhibit an extracagelocation of the alkali-metal cations, which enables the interconnectivity of neighboring cages into 1D, 2D, or 3D coordinationpolymer architectures. The unique feature of such architectures is a realization of metallocene Cs···π (Rb···π) joints, providing tightlyconnected nonporous coordination polymers. A topological classification of cages and coordination polymer networks wasperformed. Some of the obtained compounds also represent the first examples of Rb-containing silsesquioxanes. The selectedproducts were also tested as homogeneous catalysts in the oxidation and hydrocarboxylation of C 5−C 8 cycloalkanes. This studyextends the structural types of heterometallic silsesquioxane cages that can be efficiently applied to the design of functionalcoordination polymers.
- Добавил в систему: Астахов Григорий Сергеевич
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