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Communication Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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[Ag2M(Te2O5)2]SO4 (M = CeIV or ThIV): A New Purely Inorganic d/fHeterometallic Cationic Material Todd N. Poe,† Frankie D. White,‡ Vanessa Proust,‡ Eric M. Villa,§ and Matthew J. Polinski*,† †

Department of Chemistry and Biochemistry, Bloomsburg University of Pennsylvania, 400 East Second Street, Bloomsburg, Pennsylvania 17815, United States ‡ Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, Florida 32306, United States § Department of Chemistry, Creighton University, 2500 California Plaza, Omaha, Nebraska 68178, United States S Supporting Information *

efforts have been made toward the design of both new and functional inorganic cationic materials.1 Until recently, inorganic cationic materials were largely represented by the naturally occurring layered double hydroxides6,7 and the mineral Francisite.8 Both of these minerals have limited-to-no anionic exchange capabilities and, thus, have found little industrial use. More recent examples include (i) heavy pblock metal fluorides and oxides,1,9−13 such as [Pb2F2]X (X = succinate or glutarate) and [Sb4O4(OH)2]X (X = ethanedisulfonate), (ii) tetravalent f-block metal (Ce and Pu) tellurites,14,15 such as [Ce2Te7O17]X2 (X = Cl or Br) and [M2Te4O11]X2 (X = Cl or Br), and (iii) a tetravalent thorium borate ([ThB5O6(OH)6][BO(OH)2]·2.5H2O, which selectively exchanges the borate anion for the pertechnetate anion.16,17 We have recently undertaken an effort to synthesize functional inorganic cationic materials using high-valent d and f-metals with tellurite owing to the success of recently produced cationic species (vide supra). The initial focus has been on the use of tetravalent f-elements (i.e., Ce and Th) because this provides the highest stable oxidation state possible for a 4f lanthanide metal and the highest oxidation state for a 5f actinide metal which does not lead to the formation of the actinyl unit under aqueous conditions. Tellurite anions are known to have high polarizability and form unique structural topologies. Their variable coordination modes are due to the stereoactive lone pair (SALP) of electrons on the TeIV metal centers.14,15,18−25 Several studies have suggested that the presence of SALP electrons in oxoanion systems is ideal for the formation of cationic materials because they yield highly distorted metal centers with the O atoms pushed off to the sides.1,26 These observations give this system many favorable attributes for the formation of cationic materials. Herein, we report on the hydrothermal preparation and structural elucidation of a new purely inorganic d/f-heterometallic cationic material, [Ag2M(Te2O5)2]SO4 (M = CeIV or ThIV). The title compounds were synthesized using the metal oxides (MO2 and TeO2), silver nitrate, and sulfuric acid under mild hydrothermal conditions. While CeIII is the preferred oxidation state under acidic conditions (the CeIV/CeIII redox potential is 1.28 vs NHE in 1 M HCl), stabilization of CeIV can be attributed to tellurite complexation and a solubility-driven mechanism,

ABSTRACT: Two new isotypic d/f-heterometallic purely inorganic cationic materials, [Ag2M(Te2O5)2]SO4 (M = CeIV or ThIV), were synthesized using the metal oxides (MO2 and TeO2), silver nitrate, and sulfuric acid under mild hydrothermal conditions. The prepared materials were characterized via single-crystal X-ray diffraction, which revealed that the materials possess a 3D framework of corner-sharing Te2O52− units. The tellurite framework creates four unique pores, three of which are occupied by the MIV and AgI metal centers. The tellurite network, metal coordination, and total charge yield a cationic framework, which is charge-balanced by electrostatically bound sulfate anions residing in the largest of the four framework pores. These materials also possess AgI in a ligand-imposed linear geometry.

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ationic materials are a rare class of compounds that defy the usual mode of structural formation. Typically, extended networks possess an overall neutral or negative charge, where charge balance is achieved by cations residing in pores, cavities, and/or interlayer spaces. Cationic materials, however, possess positively charged chains, sheets, or frameworks, which are then charge-balanced by anions trapped in pores, cavities, and/or interlayer spaces.1 The rarity of cationic materials is generally attributed to the ratio of positive metal charge to negative ligand charge within the building units that make up the networks.1 Anions, specifically polyatomics, are usually larger than cations and the closest packing of anions within most inorganic compounds dictates the overall structure. However, if highoxidation-state metals are used in conjunction with neutral and/ or low-charged ligands, the total positive charge may be greater than the total negative charge in the framework, yielding a cationic material. Cationic materials can serve as functional anionic exchange materials if the electrostatically bound anions are labile and can be replaced by other anions in solution without compromising the integrity of the material. While industrial and environmental agencies use a wide range of polymer-based materials for anionic trapping, polymer-based materials often have a narrow range of stable operating conditions in which they can appropriately function.2−5 With a real need for more diverse exchange materials that are operational under variable conditions, great © XXXX American Chemical Society

Received: February 25, 2018

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DOI: 10.1021/acs.inorgchem.8b00504 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry which has been reported elsewhere.27−29 The products consisted of orange (Ce) or colorless (Th) column-shaped crystals (Figures S1 and S3) along with minor impurities of unreacted starting materials. It should be noted that using other starting felement sources, such as MCl3, or other strong acids failed to produce the title compounds. Single-crystal X-ray diffraction studies reveal that [Ag2M(Te2O5)2]SO4 crystallizes in the centrosymmetric, orthorhombic space group Cmca and is a porous 3D framework (Figure 1 and

Figure 3. Depiction of (a) the Te2O52− units that edge-share to create (b) a 2D tellurite sheet with large rectangular cavities in the [ac] plane in which the SALP electrons on Te reside. (c) When viewed stacked with another sheet on top the first, new coordination sites for (1) Ce/Th, (2) linear Ag, (3) distorted trigonal-planar Ag, and (4) sulfate become apparent. (d) MO8 square-antiprismatic geometry showing the coordination of Te2O52− units to MIV centers.

are able to form 1D chains, 2D layers, and/or 3D frameworks by binding between three and five O atoms.19 The main scaffold of the title compounds is comprised of Te2O52− units that cornershare to form a 2D sheet extending into the [ac] plane (Figure 3). These sheets possess approximately 4.5 Å × 8.0 Å rectangular cavities that house the SALP electrons which reside on top of the Te metal centers. When a second 2D tellurite sheet is placed on top of the first, four new cavities become apparent which allow for the coordination of Ce/Th and Ag and the electrostatically bound sulfate anion (Figure 3c). The MIV metal centers are coordinated by four Te2O52− units in which two of the units edge-share and two units corner-share to the metal providing the M−O bonds (Figure 3d). The M−O bond lengths are in the ranges 2.290(4)−2.377(4) and 2.357(6)−2.426(6) Å for the Ce and Th compounds, respectively (Table S2). The overall cationic framework allows for sulfate anions to be electrostatically bound and occupy the largest of the four pores present in the framework (Figure 3c); these sulfate anions provide charge balance for the structure. This sulfate-containing cavity is formed by the tellurite units oriented such that the SALP electrons point toward the center of the cavity. The positive charge of the framework is a result of the structure containing a tetravalent f-block metal (CeIV or ThIV) as well as two unique dblock metals (AgI). These f-block metal centers are bound to a low overall charged tellurite ligand (Te2O52−) and have a high propensity to polymerize. The charge from the tellurite network is balanced out by the tetravalent f-element center because of coordination of two Te2O52− units for every MIV center (Figure 3d). Therefore, the net 2+ charge of the framework comes from the coordinated AgI cations which fill in the other cavities of the framework (Figures 3c and 4). The Ag atoms possess two different coordination geometries: linear and distorted trigonal planar (Figures 2 and 4). Ag is known to possess a wide range of coordination numbers (2−7). These variable coordination modes are a result of no crystal-field stabilization of the d10 configuration. While no geometric preferences for Ag exist, a coordination number of 2 is typically observed because of restrictions imposed upon it by the ligand.30−35 The linear AgI centers reside in pores created by the tellurite scaffold (Figures 3c and 4) and are coordinated by

Figure 1. Depiction of the 3D framework of [Ag2M(Te2O5)2]SO4 (M = CeIV or ThIV) viewed down the b axis. The Ce and Th centers are represented by the orange polyhedra, Te2O52− anions are represented by the olive polyhedra, the purple spheres represent linear Ag units, the gray spheres represent distorted trigonal-planar Ag units, and the yellow polyhedra represent sulfate anions.

Table S1). Energy-dispersive spectroscopy (EDS) measurements, which provide elemental analysis data, also support the chemical formula (Figure S2). [Ag2M(Te2O5)2]SO4 is constructed from MO8 square antiprisms, both linear and distorted trigonal-planar AgI centers, SO42− tetrahedra, and Te2O52− units comprised of two TeO32− trigonal-pyramidal polyhedra corner sharing via an O atom (Figures 1−3). Tellurites (TeIV) have wide-ranging structural chemistry because of their SALP electrons as well as their varied coordination abilities. Tellurites

Figure 2. Coordination geometries for the metals and S atoms in [Ag2M(Te2O5)2]SO4 (M = CeIV or ThIV): (a) square-antiprismatic geometry of Ce/Th; (b) linear geometry of Ag; (c) distorted trigonalplanar geometry of Ag; (d) tetrahedral geometry of S. B

DOI: 10.1021/acs.inorgchem.8b00504 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

ThIV), were hydrothermally synthesized. The title compounds were constructed from tellurite building blocks, which link to form Te2O52− units, which further polymerize to form a 3D porous framework. The framework is composed for four different pores that house the MIV metal centers in a square-antiprismatic geometry and AgI metal centers in both linear and distorted trigonal-planar geometries. The final pore of the framework contains the electrostatically bound sulfate anion. Preliminary studies suggest that the electrostatically bound sulfates can be exchanged for other anions in solution. Investigations are underway to determine the anion-exchange abilities of these compounds.

Figure 4. Depiction of the pores in which (a) the linear and (b) trigonalplanar AgI cations reside. The CeIV and ThIV centers are represented by the orange polyhedra, the Te2O52− units are represented by the olive polyhedra, the purple spheres represent linear Ag units, the gray spheres represent distorted trigonal-planar Ag units, and the red spheres represent O atoms.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b00504. Experimental details, X-ray crystallographic data, solidstate UV−vis−near-IR spectra, bond-valence-sum calculations, scanning electron microscopy images, and EDS (PDF)

two symmetry-related O2 atoms at a distance of 2.209(4) and 2.217(7) Å for the Ce and Th structures, respectively. The bond angles are 180° (Table S2). The other O atoms making up this pore range in distance from 2.883 to 2.971 Å from the Ag site, rendering them too far to be considered as reasonable bonds. The distorted trigonal-planar Ag is coordinated to two symmetry-equivalent O5 atoms and an O6 atom at distances of 2.315(4) and 2.423(6) Å for Ce and 2.314(7) and 2.489(10) Å for Th (Table S2). The bond angles are 103.30° and 127.34° for Ce and 102.58° and 127.74° for Th. The other O atoms making up this pore range in distance from 2.784 to 3.479 Å from the Ag site, rendering them too far to be considered as reasonable bonds. The variability in the coordination geometries about the metal centers in these compounds is due to the flexible coordination modes of the metals used. The structural chemistry of f-element complexes is diverse because of both high coordination numbers and a lack of geometric preference. It is typical for f-elements to have coordination numbers of 6−10; within each exist several different coordination modes.36−38 For example, f-elements with a coordination number of 8 can have the geometries of a cube, dodecahedron, hexagonal bipyramid, bicapped trigonal prism, and square antiprism (as observed in this work).36−38 Ag can have coordination numbers of 2−7 depending on the flexibility of the ligand.30 Tellurium, because of its SALP electrons and polarizability, can form polymeric structures, resulting in highly variable coordination environments. This is due to tellurium’s ability to bind three, four, or five O atoms and form a variety of building units such as 1D chains, 2D sheets, and 3D frameworks.14,15,19−25 One of the most interesting aspects of the structure is that it is a purely inorganic cationic framework. Inorganic cationic frameworks may serve as functional anion-exchange materials that can operate in more chemically extreme environments (i.e., radioactive, highly acidic/basic, oxidizing, etc.) than their organic cationic counterparts. For the title compounds, preliminary studies suggest that these materials possess the ability to exchange their electrostatically bound sulfate anions for other anions in solution without compromising the integrity of the framework. This is in stark contrast with the other tetravalent cerium tellurite cationic materials previously reported.14,15 Additional studies are underway, and the results of the exchange ability of the title compounds will be reported elsewhere. To the best of our knowledge, the Ce compound represents the third Ce-containing inorganic cationic framework. In conclusion, two new isotypic d/f-heterometallic purely inorganic cationic materials, [Ag2M(Te2O5)2]SO4 (M = CeIV or

Accession Codes

CCDC 1819474−1819475 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (M.J.P.). ORCID

Matthew J. Polinski: 0000-0002-3789-9414 Author Contributions

All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS T.N.P. and M.J.P. acknowledge Bloomsburg University of Pennsylvania for financial support. E.M.V. acknowledges Creighton University for financial support. F.D.W. acknowledges Florida State University for financial support. V.P. performed optical measurements and was supported, in part, by the Center for Actinide Science and Technology, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DESC0016568.

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REFERENCES

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DOI: 10.1021/acs.inorgchem.8b00504 Inorg. Chem. XXXX, XXX, XXX−XXX