Tridecanuclear Cu 11Na2 cagelike silsesquioxanes. - ACS Publications

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Tridecanuclear CuII11Na2 cagelike silsesquioxanes Grigorii S. Astakhov, Alexey N. Bilyachenko, Mikhail M. Levitsky, Alexander A. Korlyukov, Yan V. Zubavichus, Pavel V. Dorovatovskii, Victor N. Khrustalev, Anna V. Vologzhanina, and Elena S. Shubina Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00778 • Publication Date (Web): 09 Jul 2018 Downloaded from http://pubs.acs.org on July 10, 2018

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Crystal Growth & Design

Tridecanuclear CuII11Na2 cagelike silsesquioxanes. Grigorii S. Astakhov,†,‡ Alexey N. Bilyachenko,*†,‡ Mikhail M. Levitsky,† Alexander A. Korlyukov,‡,§ Yan V. Zubavichus,∥ Pavel V. Dorovatovskii,∥ Victor N. Khrustalev,‡,∥ Anna V. Vologzhanina,† Elena S. Shubina† †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 §Pirogov Russian National Research Medical University, Ostrovitianov str., 1, 117997 Moscow, Russia ∥National Research Center “Kurchatov Institute”, Akademika Kurchatova pl., 1, 123182 Moscow, Russia

ABSTRACT. A series of three unprecedented heterometallic copper(II)sodiumsilsesquioxanes were isolated (i) via the unusual rearrangement process during synthesis of coordination polymers or (ii) via the self-assembly reaction using 2,2’-bipyridine. The unique type of these products molecular topology consists of an unusual fusion of two sandwich-like components

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(each including five copper and one sodium sites) via a central copper ion. These compounds correspond to the highest nuclearity among Cu(II)-based cage silsesquioxanes reported to date.

Introduction The design of different types of coordination polymers attracts a huge deal of attention from different research teams worldwide. This can be explained both by numerous types of emerging products as well as by a wide range of prospective applications of such non-trivial substances.1 Among different types of building blocks used for the design of coordination polymers, cagelike metallasilsesquioxanes2-3 still remain rare. The reported synthetic strategies giving rise to metallasesquioxanes’ supramolecular architectures concern the variation of the nature of external alkaline metal ions and/or nature of solvating ligands linking neighboring cage units.2-3 An independent approach implies the aggregation of unusual MOFs via interaction of octasilsesquioxanes and metal halides.4 In turn, an alternative approach, vis., the use of dicarboxylic acids as bridging linkers in the metallasesquioxane’ coordination polymers design has remained totally ignored. Importantly, truly enormous amount of “non-metallasesquioxane” coordination polymers were successfully developed following this “dicarboxylic” approach. This method allowed the assembly of various products including wide range of metal ions, namely, (i) main group5-7, (ii) transition,8-10 (iii) lanthanides and actinides.11-14 Several important properties were recently reported for copper-based coordination polymers designed on dicarboxylic building blocks, vis. H2 adsorption,15 development of electrode materials for supercapacitors,16-17 molecular magnetism.17 Taking these results in mind, as well as broadly known proneness of copper-based silsesquioxanes towards assembly of a variety of molecular architectures18-21 with distinguished catalytic activity,20, 22-23 we were interested in studies of possible “dicarboxylic


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acid’ linking” of coppersilsesquioxanes. For the starting material, a cagelike globular CuII4Na4phenylsilsesquioxane24 was chosen due to simplicity of its synthesis and robustness of the structure surviving numerous procedures of solvating ligand replacement and transmetalation of sodium ions, reported by some of us recently.25 Two types of dicarboxylic compounds, namely, terephthalic and 2,6-naphthalenedicarboxylic acids, were chosen as potential linkers. The choice of acids is quite explainable due to numerous reports (e.g., Refs 26-31 for terephthalic acid and Refs 32-38 for 2,6-naphthalenedicarboxylic acid) confirming ultimate efficiency of these linkers in the design of various coordination polymers including MOFs.

RESULTS AND DISCUSSION Here we present unexpected results of our very first effort into the synthesis of metallasilsesquioxane-based coordination polymers through the interaction with two types of dicarboxylic compounds, namely, terephthalic and 2,6-naphthalenedicarboxylic acids (Scheme 1). To our surprise, these reactions gave truly surprising results. Namely, instead of expected linking of starting globular CuII4Na4-phenylsilsesquioxane moieties by dicarboxylic acids, we observed an intriguing structural rearrangement resulted in the formation of mixed-metal CuII11Na2 cage phenylsilsesquioxanes 1 and 2.


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Scheme 1. Preparation of Cu11Na2-phenylsislsesquioxanes (1 and 2) via self-assembly in the presence of terephthalic and 2,6-naphthalenedicarboxylic acid, respectively. Formation of coordination polymer’ copper(II) 2,6-naphthalenedicarboxylate 3, as a side product in the synthesis of 2.

Importantly, the molecular topology of products was found quite similar (Figure 1) for both runs of the reaction (with terephthalic and 2,6-naphthalenedicarboxylic acids) and the difference between compounds 1 and 2 essentially relates to solvating ligands either DMF (for 1) or pyridine (for 2). Such a difference in solvation induces some variation of structural parameters (presented in Figure 2).


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Figure 1. Molecular structures of cage Cu11Na2-phenylsilsesquioxanes 1 and 2. Color code: Si – light-yellow, O – red, Cu – tourquoise blue, Na – yellow, N - blue.


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Figure 2. Simplified view of Cu11Na2-based complexes 1-2 (according to X-ray diffraction studies). Several bond lengths (in Å) are shown to emphasize slight variations in their structural parameters. The type of molecular architecture found in 1-2 is very unusual. First of all, these complexes correspond to the highest nuclearity among all Cu(II)-silsesquioxanes reported to date (note that the giant Cu24-silsesquioxane reported by team of H. Zhu and H.W. Roesky19 included Cu(I) ions only). Other examples of Cu-based cage silsesquioxanes, reported clusters of lower nuclearity (e.g. Cu4 by F. T. Edelman team,18 Cu2 and Cu6 by C. Limberg team,21 Cu4 and Cu10 by A. A. Korlyukov team2). Both in terms of composition and structure, complexes 1-2 are completely different from all types of reported Cu-silsesquioxanes.2-4,18-21


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First of all, the location of copper ions in the cage moiety of products 1-2 is no doubt an unique one. One could observe two Cu5-containing layers with a central copper ion serving as a pivot point in the connection of two unusual Si10-based silsesquioxane fragments (Figure 3, top). Each Si10-fragment includes two types of ligands – cyclic [PhSiO1.5]6 and acyclic [PhSiO1.5]4 silsesquioxanes (Figure 3, bottom). The latter, being non-condensed, enables that extraordinary fusion of two Cu5-based fragments via the eleventh copper ion. Note, ligands with the [RSiO1.5]4 composition are very rare among reported cage metallasilsesquioxanes structures, being observed for Mn-39 and Ti-based40 silsesquioxanes.


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Figure 3. Top. The undecacopper clusters in 1-2 connected by bridge atoms. Bottom. The structure of silsesquioxane ligands in 1-2: condensed [PhSiO1.5]6 and non-condensed [PhSiO1.5]4. Color code: Si – light-yellow, O – red, Cu – tourquoise blue. The resulting undecacopper cluster can be regarded as a cluster of two condensed six-membered rings with the bridge copper atom deviating from the ring planes. It contains three types of twoconnected metal atoms, and one metal atom connected via oxygen atoms with four other metal atoms, thus, it belongs to 2,2,2,4-M11 clusters, wherein M denotes a discrete cluster and k = 11 is the total number of metal atoms in the cluster.41 Note, that such clusters are absent in the TTD collection42 of topological types of clusters found in 19414 previously reported compounds. Thus, we received not only a novel silsesquioxane, but also a polynuclear complex with novel skeleton of metal cluster.


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Regarding the mechanism of formation of these non-trivial products 1 and 2, it is important to emphasize that neither terephthalic nor 2,6-naphthalenedicarboxylic acid were found in the final composition of corresponding products. This fact resembles the so-called “silent witness” effect, recently presented by some of us for Cu7-silsesquioxane clusters.43 The term “silent witness” means unambiguous participation of an extra reactant during synthetic reaction without entering final product’ composition. Ref. 43 describes the isolation of Cu7-clusters (instead of classical Cu6 cages) due to the presence of “silent” amides. In the present work, dicarboxylic acids apparently act in a similar manner providing the formation of compounds 1 and 2 with a nuclearity type, which has never been observed before. We may conclude that the role of dicarboxylic acids as route-governing reaction components could not be denied. For instance, self-assembly reactions under similar conditions (at the absence of dicarboxylic acids) gave exclusively Cu5- (for pyridine media)3,44 or Cu6-silsesquioxanes (for DMF media).3,45 Such a “acid addition” effect giving rise to products 1-2 seems to be a novel approach as applied to cage metallasilsesquioxanes. Most probably, the reaction route involves multiple opportunities for the ligation of metal ions by silsesquioxane moieties and dicarboxylic acids. For example, under synthesis conditions used for 2, we also succeeded in the isolation of corresponding salt, copper(II) 2,6-naphthalenedicarboxylate 3, featuring a coordination polymer structure (Scheme 1, Figure 4).


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Figure 4. Molecular structure of copper(II) salt of 2,6-naphthalenedicarboxylic acid 3 (pyridine solvate). Color code: Cu – turquoise blue, O – red, N - blue.

In turn, the composition of silsesquioxane ligands of products 1-2 ([PhSiO1.5]6 and [PhSiO1.5]4) is principally different to composition of ligand of a starting globular metallasilsesquioxane ([PhSiO1.5]12). It implies that the mechanism of complexes 1-2’ formation should be regarded as a complicated multi-stage rearrangement. We believe that this process includes (i) decoordination of ([PhSiO1.5]12) ligand from metal centers in the starting metallasilsesquioxane followed by (ii) competitive coordination of metal ions by dicarboxylic units and silsesquioxane ligands with ([PhSiO1.5]6 and [PhSiO1.5]4) compositions generated in situ. Thus the solution after the reaction is a mixture of Cu,Na-phenylsilsesquioxane and dicarboxylic salt units. Due to strong paramagnetism of both components, the isolation and study of products in the single crystal form appropriate to X-ray crystallography are strongly required. It is known though that the crystallization of cage metallasilsesquioxane is not a very simple task. Indeed, we succeeded


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in the isolation of crystalline material of all products 1-3 only in low yields (9%, 12%, 20% respectively). The fact that dicarboxylic components, despite their involvement in the reaction mechanism, are not present in the products’ composition prevents a straightforward choice of the reactants ratio metallasilsesquioxane/acid. In order to improve on the Cu11Na2-molecular architecture’ yield we choose an alternative approach. In our opinion, bidentate ligand, 2,2’bipyridine (which has been successfully applied by some of us for the synthesis of metallasilsesquioxanes of Si10Cu6N4 composition46-47), could also be an efficient reactant for the synthesis of Si20Cu11Na2 architecture, similar to 1 and 2, even without use of dicarboxylic acids. Indeed, this directed reaction including PhSi(OEt)3, CuCl2 and 2,2’-bipy as components of the self-assembly process allowed us to gain more control/predictability over the synthesis and to obtain compound 4, which can be regarded as an apparent trade-off between Cu11Na2-topology of products 1-2 and complexation with 2,2’-bipyridine ligands (Scheme 2, Figure 5, left). The yield of the compound (28% for the dried crystalline material) is moderately high for cage metallasilsesquioxanes. Supposed mechanism for the assembly of compounds 4 (as well as compound 1) is given in the ESI (Figures S1-2). In general, compound 4 belongs to structural family of complexes 1 and 2. Nevertheless, some differences between them should be mentioned. First, only two possible positions at copper sites in 4 are occupied by 2,2’-bipyridines, while other ones coordinate neither ligands nor solvates. This causes some deviation of geometrical parameters with respect to compounds 1-2 (see Figure 2 and Figure 5, right).


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PhSi(OEt) 3 NaOH CuCl2

bipy MeCN

O O O O O PhSi PhSi PhSi PhSi PhSi O

O

Cu

N

Cu

N O PhSi O

O

O

Cu

Cu

O

SiPhPhSi PhSi

Cu

O

O

O

O O Cu

Na N O

O

PhSi PhSi O O

N Na

Cu

O

O

SiPh

O

O

O

O

O

O

O

SiPhSiPhPhSi

SiPh

O

O

O

Cu

Cu

O

O

O

N

Cu Cu O

SiPh SiPh PhSi O O O

[MeCN] 4

N

O SiPh O

4

Scheme 2. Self-assembly phenylsislsesquioxane 4

of

PhSi(OEt)3,

CuCl2

and

2,2’-bipy

into

Cu11Na2-

Figure 5. Left: Molecular structure of cage Cu11Na2-phenylsilsesquioxane 4. Color code: Si – light-yellow, O – red, Cu – tourquoise blue, Na – yellow, N – blue. Right: Simplified view of complex 4 with several bond lengths shown (in Å).


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Regarding geometries of Cu11-based complexes 1-2 and 4 in general, it should be noted that complexes 1 and 2 are characterized by the same motif of copper ions’ surrounding realized by the involvement of six DMF (product 1) or pyridine (product 2) molecules. To the contrary, compound 4 is characterized by a much higher content of tetracoordinated copper sites (8 vs. 4 for 1 or 2, Figure 6). This could be of interest taking into account the significant prospect of copper-based complexes in catalysis.3, 19-20, 22-23, 43, 46-52 In turn, structural parameters of central fragment Na-O(O)-Cu-O(O)-Na are almost the same for all products 1-2 and 4. Even despite replacement of solvating ligand (DMF for 1, Py for 2, MeCN for 4), the Na-Cu distance is quite close to 3.50 Å (Figure 7).


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Figure 6. Difference in the coordination surrounding of copper ions in 1-2 and 4

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4 Figure 7. Influence of solvating ligands on structure of central Na-O(O)-Cu-O(O)-Na unit in 1-2 and 4. Color code: Si – light-yellow, O – red, Cu – tourquoise blue, Na – yellow, N – blue.

The same behavior is characteristic for Na sites of Cu5-layers (Figure 8). An influence of solvating ligand’ nature on structural parameters of Na-O(O)-Cu-O(O)-Na units is negligible (the Na-Cu distance is quite close to 3.30 Å). In turn, replacement of monodentate ligand (DMF for 1, Py for 2) by bidentate one (2,2’-bipyridine for 4) strongly influence the location of the copper ion, coordinated by corresponding ligand. The Cu-Cu distance between this copper ion and the neighboring one is quite similar for 1 and 2 (2.83 Å and 2.81 Å, respectively). In case of 4 one could mention significant withdrawal of external Cu ion from the cage skeleton (Cu-Cu = 3.29 Å).


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1

2

4

Figure 8. Influence of ligand on structural parameters of Cu5Na unit in 1-2 and 4. Color code: Si – light-yellow, O – red, Cu – tourquoise blue, Na – yellow, N – blue


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Thus, we present here a novel approach to high-nuclearity Cu11Na2 cage phenylsilsesquioxanes via the unusual rearrangement process during synthesis of coordination polymers on the base of Cu-silsesquioxanes. Both strategies – creation of high-nuclearity metallasilsesquioxanes and metallasilsesquioxane-based coordination polymers seem to be highly promising for the progress of the synthetic chemistry. Corresponding investigations are currently underway.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: XXX General methods, tables for the results of single crystal data and elemental analysis, extra figures, IR and UV spectra, X-ray data in CIF format (CIF).

Accession Codes CCDC 1835135-1835138 contain the supplementary crystallographic data for this paper. These data can be obtained free of e-mailing [email protected], or by contacting The Cambrige Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, U.K.; fax: +44 1223 336033

AUTHOR INFORMATION Corresponding Author * E-mail: [email protected]


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Notes The authors declare no competing financial interests.. ACKNOWLEDGMENT The work was accomplished with the support of the “RUDN University Program 5-100” and funded by RFBR according the research projects 16-03-00206, 17-03-00993. Synchrotron singlecrystal 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 Tridecanuclear CuII11Na2 cagelike silsesquioxanes G. S. Astakhov, A. N. Bilyachenko*, M. M. Levitsky, A. A. Korlyukov, Y. V. Zubavichus, P. V. Dorovatovskii, V. N. Khrustalev, A. V. Vologzhanina, E. S. Shubina 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 Pirogov Russian National Research Medical University, Ostrovitianov str., 1, 117997 Moscow, Russia National Research Center “Kurchatov Institute”, Akademika Kurchatova pl., 1, 123182 Moscow, Russia

Three unprecedented Cu(II)/Na-silsesquioxanes were isolated and characterized. The unique type of their molecular topology consists of a fusion of two sandwich-like components (each including five copper and one sodium sites) via a central copper ion. These compounds correspond to the highest nuclearity among Cu(II)-based cage silsesquioxanes reported to date.


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Tridecanuclear Cu 11Na2 cagelike silsesquioxanes. - ACS Publications

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