High-Nuclearity (Cu8-Based) Cage Silsesquioxanes: Synthesis and

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High-nuclearity (Cu8-based) cage silsesquioxanes: Synthesis and structural study Alexey N. Bilyachenko, Victor N. Khrustalev, Yan V. Zubavichus, Anna V. Vologzhanina, Grigorii Astakhov, Evgenii Ivanovich Gutsul, Elena S. Shubina, and Mikhail M. Levitsky Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00082 • Publication Date (Web): 05 Mar 2018 Downloaded from http://pubs.acs.org on March 7, 2018

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Crystal Growth & Design

High-nuclearity (Cu8-based) cage silsesquioxanes: Synthesis and structural study Alexey N. Bilyachenko,*,†,‡ Victor N. Khrustalev,‡,§ Yan V. Zubavichus,§ Anna V. Vologzhanina,† Grigorii S. Astakhov,†,‡ Evgenii I. Gutsul,† Elena S. Shubina,† and Mikhail M. Levitsky† †

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov

Str., 28, 119991 Moscow, Russia ‡

Peoples’ Friendship University of Russia, Miklukho-Maklay Str., 6, 117198 Moscow, Russia

§

National Research Center “Kurchatov Institute”, Akademika Kurchatova pl., 1, 123182

Moscow, Russia

ABSTRACT: We herein report a study of Cu(II)-silsesquioxanes’ self-assembly in the presence of two possible template agents (acetonitrile and acetone). This results to the isolation of unusual high-nuclearity cluster CuII8 cage silsesquioxanes [(Ph8Si8O16)2 Cu8 (DMF)8] [Ph8Si8O12] . 2MeCN 1 and [(Me8Si8O16)2 Cu8 (Me2CO)4]2 [MeCOO-]2 [Na+]2 . 2(H2O) . 3(Me2CO) 2. In the case of 1, acetonitrile indeed serves as a template being incorporated into the inner void of the prism-like cage of the crystalline product. To the contrary, in the case of complex 2, acetone molecules just play the role of external solvates. Inner void of the prism-like cage in 2 is occupied by sodium acetate groups. The latter, most likely, are produced via the mild oxidation of ethanol during the synthesis of 2. Finally, sodium centers of these acetate groups caused an unprecedented “cage connectivity” (dimerization of two octacopper cage silsesquioxanes in 2).

Unusual representatives of cage metallacomplexes, namely, cage-like metallasilsesquioxanes1-5 (CLMSs), are a worldwide hot research topic being developed by numerous research teams due

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to a variety of synthetic approaches6-10 to such compounds, their structural multitude,11-13 intriguing magnetic (spin glass)14-18 properties and potential applications. Among potential applied fields, catalysis,19-25 production of brush-like polymer materials,26-29 membranes,30 nanoparticles,31 coordination polymers10,

18, 32-34

and calcined inorganic materials35-37 could be

mentioned. One of widespread geometries of CLMSs is a prism-like architecture with parallel layers - one metal oxide (M-O-M) and two siloxane (Si-O-Si) ones (Figure 1, left). By now, the number of compounds belonging to this structural type exceeds 30, according to the CCDC database.5 Along with differences in the nature of (i) metal ions incorporated in the siloxane matrix (ii) substituents at silicon atoms, and (iii) solvating ligands, the CLMSs differ from each other in the cage nuclearity. Usually, the CLMSs are hexanuclear (M)6, containing a pair of [RSiO]6 ligands.5, (M)515,

17, 39-40

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In turn, several examples of prismatic cage silsesquioxanes of a lower

or higher, (M)7,41 (M)842 and (M)9,43 nuclearity have been reported. Small

molecules present in the synthesis as a solvent or ligand, such as pyrazine42 or dimethyl sulfoxide,43 were localized in the inner prismatic voids of the target cages and thus were regarded as specific template agents governing the “high nuclearity shift”, i.e., directed assembly of a CLMS with an increased nuclearity (Figure 1, right). By design, this phenomenon is similar to a well described ability of polyhedral oligosilsesquioxanes to capture a fluoride anion.44-48 According to these observations, one could suggest that CLMS can encapsulate other species as well, which would give rise to previously undiscovered principles underlying the structure formation for these intriguing compounds. As an implementation of this work, we herein demonstrate

how

other

small

molecules

could

govern

the

aggregation

of

cage

metallasilsesquioxanes. In this paper, acetonitrile and acetone (both are known for their encapsulation properties49-51) were studied in the context of their potential effects exerted on the


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nuclearity of emerging Cu(II)-based silsesquioxanes. We have performed parallel self-assembly reactions starting from triethoxysilanes bearing different (Me or Ph) substituents at the silicon atoms. According to our expectations, this would allow one to evaluate possible substituents’ steric effects. At the first stage of the reaction, some of Si-OEt groups of silanes were converted into reactive silanolate Si-ONa groups by the interaction with NaOH (ratio Si/Na = 1/1). At the second stage, these silanolates were put into reaction with CuCl2 (ratio Na/Cu = 2/1) in different solvent media in the presence of aforementioned acetonitrile and acetone as small-molecule templates. Noteworthy alcohol that acted as a reaction medium during the silanolate’s formation was not removed from the reaction mixture upon completion of the first stage of synthesis. It does not seem too surprizing due to results published by some of us in recent work43 reporting on a nonanuclear coppersilsesquioxane encapsulating a DMSO molecule in its center. This unusual process occurred in the presence of both DMSO and alcohol solvent molecules in the reaction medium. Thus, we could expect a similar displacement of alcohol molecules in the final product stoichiometry after addition of acetonitrile or acetone. According to this, the deliberate removal of alcohol was not obligatory since it gives us an opportunity to evaluate competition of different potential solvating ligands during the cage metallasilsesquioxane’ assembly. Two of these reaction conditions, namely, (i) the transformation of phenyltrietoxysilane in the presence of acetonitrile (Figure 2. top) and (ii) the transformation of methyltrietoxysilane in the presence of acetone (Figure 3, top), were found successful for the isolation of novel crystalline products. A slow evaporation of solvents allowed us to obtain blue in color CLMSs 1 (24% yield) and 2 (19 % yield), respectively.


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Figure 2. Top. General scheme of synthesis of compound 1 in the presence of acetonitrile. Bottom. Solid state structure of 1. Color code: Si – yellow, O – red, Cu – turquoise green, N – blue. DMF solvates coordinating copper ions at external positions are not shown for clarity.


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Figure 3. Top. General scheme of synthesis of compound 2 in the presence of acetone. Bottom. Solid state structure of 2. Color code: Si – yellow, O – red, Cu – turquoise green, Na – orange, N – blue.

Both structures 1 and 2 are exclusively unusual as compared to any known molecular geometries of CLMSs. First of all, products 1-2 add up to a very rare family of octanuclear cage silsesquioxanes (the first and the only type of compound of such an unusual nuclearity was obtained using pyrazine as a template center42). Note, that despite the difference in steric characteristics of starting silanes (MeSi vs. PhSi), similar Cu8-cores were found in the composition of both products. In the case of CLMS component of compound 1, the role of the template center is played by an acetonitrile molecule (Figure 2, bottom), which is a brand new feature in the regulations underlying the CLMS assembly process. Another remarkable feature of product 1 is the fact of cocrystallization of CLMS and metal-free octaphenyloctasilsesquioxane (PhT8) in a common supramolecular architecture. To the best of our knowledge, this is the very


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first observation of such a mixed crystal, despite significant attention paid to chemistry and structures of polyhedral oligosilsesquioxanes.52-58 Note, that we succeeded in the crystallization of complex 1 from acetonitrile/DMF system and DMF solvates coordinate copper ions outside the cage. Thus, one could conclude that DMF, known as a ligand with high coordination affinity, also strongly influences the assembly process of the Cu8-core. Here we would like to cite an earlier work by S. V. Lindeman team,59 devoted to the synthesis of Cu(II)-based phenylsilsesquioxane in the DMF-only system. This results in the formation of a product with the principally different, Cu6, nuclearity. Thus, we should emphasize the role played by acetonitrile during the formation of complex 1, especially taking in mind its obvious proneness to encapsulation. In the case of product 2, acetone molecules did not enter the inner prismatic void of the cage occupying exterior solvation positions. Thus, the templating effect of acetone is not as evident as in the case of compound 1. Nevertheless, cage component of complex 2 (crystallized from acetone/ethanol mixture) is still capable of forming an unusual high-nuclearity octanuclear cage. Similarly to the above discussion regarding product 1, it is worth mentioning that numerous “alcohol-only” syntheses of Cu(II)-silsesquioxanes,5 never resulted in Cu8 products. This necessarily means that the role of acetone’s assistance in the assembly of product 2 should not be underestimated. We could presume some coordination of metallasilsesquioxane species and acetone molecules, favoring the formation of the Cu8 core. At the last stage of the compound 2 crystallization, acetone molecules, being weakly binding ligands, are expelled from the coordination sphere of the copper ions. As a result, the free sites are occupied by ethanol molecules. In turn, the presence of ethanol in the reaction system provoked a truly intriguing encapsulation event. The role of captured species is played herein by sodium acetate, formed in


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situ during the synthesis/crystallization. Several earlier reports implied a high oxidative potential of the metallasilsesquioxane systems. These reports included examples of (i) silsesquioxane’s metal ion oxidation (CeIII to CeIV,60 UIV to UVI,8 CrII to CrIV 61), (ii) oxidation of an N-ligand used for the metallasilsesquioxane’ assembly (neocuproine to the respective geminal diol via the hydroxylation of one of the Me groups),62 (iii) oxidation of solvent molecules used for the CLMS synthesis (ethanol to acetate,9,

63

THF to γ-butyrolactone64). Thus, the formation of sodium

acetate during the synthesis is a rare but not an unprecedented observation. In turn, to the best of our knowledge, the phenomenon of capture of acetate species by CLMS has never been reported. And even more than that, the coordination of sodium ions (balancing the charge of the acetate) to water molecules solvating the octanuclear cage component of 2 provokes an extraordinary linkage of two CLMSs. As a result, the whole structure of 2 represents a unique dimer of two octacopper cages. It is of interest to describe both structures 1 and 2 in terms of the topological analysis (Figure 4). Octanuclear metal belts in the cage components of 1 and 2 can be simplified to Cu8O16 rings. These rings realize the 2M8-1 topology (the notation described in Ref. 65 denotes the 2M8-1 clusters as follows: 2 is the coordination number of topologically inequivalent nodes, M denotes a discrete cluster, 8 is the number of metal atoms in the cluster, and 1 is the classification number to distinguish topologically distinct octanuclear clusters). At the same time, unprecedented CLMS dimerization in 2 leads to an octadecanuclear cluster (16 copper atoms, two sodium atoms and the µ2-oxygen atoms) with the 2,3,3M18-1 topology that has not occurred before.


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Figure 4. The octa- (compound 1, left) and octadecanuclear (compound 2, right) metalcontaining clusters connected by bridging oxygen atoms. The corresponding graphs of clusters’ connectivity are shown as solid black lines.

Herewith, we reported the solvent-assisted self-assembly of Cu(II)-organosilsesquioxanes giving rise to unexpected and previously undescribed octanuclear cages. Although the apparently highly important solvent effects are still poorly understood, we believe that the results reported extend the existing knowledge base to enable complete predicatability, genuine materials design and purposeful synthesis in the future.

ASSOCIATED CONTENT Supporting Information. The following information is available free of charge: details of synthetic and X-ray experiments.


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AUTHOR INFORMATION Corresponding Author Alexey N. Bilyachenko ([email protected])

Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

ACKNOWLEDGMENT The publication was prepared with the support of the “RUDN University Program 5-100” and funded by RFBR according to the research project 17-03-00993. Synchrotron single-crystal diffraction measurements were performed at the unique scientific facility Kurchatov Synchrotron Radiation Source supported by the Ministry of Education and Science of the Russian Federation (project code RFMEFI61917X0007).

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For Table of Contents Use Only. High-nuclearity (Cu8-based) cage silsesquioxanes: Synthesis and structural study Alexey N. Bilyachenko, Victor N. Khrustalev, Yan V. Zubavichus, Anna V. Vologzhanina, Grigorii S. Astakhov, Evgenii I. Gutsul, Elena S. Shubina, and Mikhail M. Levitsky

High-nuclear coppersilsesquioxanes [(Ph8Si8O16)2 Cu8 (DMF)8] [Ph8Si8O12] . 2MeCN 1 and [(Me8Si8O16)2 Cu8 (Me2CO)4]2 [MeCOO-]2 [Na+]2 . 2(H2O) . 3(Me2CO) 2 were synthesized using acetonitrile and acetone as small-molecule template agents. In 1, acetonitrile indeed serves as a template. Inner void of the cage in 2 is occupied by acetate groups produced via the oxidation of ethanol during the synthesis.


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High-Nuclearity (Cu8-Based) Cage Silsesquioxanes: Synthesis and

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