Anion-Assisted Crystallization of a Novel Type of ... - ACS Publications

Subscriber access provided by LOCK HAVEN UNIV

Communication

Anion-assisted crystallization of a novel type of rhenium(IV)-based salt Donatella Armentano, and José Martinez-Lillo Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00132 • Publication Date (Web): 09 Mar 2016 Downloaded from http://pubs.acs.org on March 9, 2016

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 6

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

Anion-assisted crystallization of a novel type of rhenium(IV)based salt Donatella Armentano*a and José Martínez-Lillo*b a

Dipartimento di Chimica e Tecnologie Chimiche (CTC), Università della Calabria, via P. Bucci 14/c, 87036, Rende (CS), Italy. bInstituto de Ciencia Molecular (ICMol), Universitat de València, C/ Catedrático José Beltrán 2, 46980, Paterna, Valencia, Spain.

Supporting Information Placeholder ABSTRACT: A novel rhenium(IV)-manganese(II) double salt

of formula (NBu4)10[{ReCl4(ox)}3Mn]2[ReCl6] (1) (NBu4+ = tetran-butylammonium cation and ox2- = oxalate dianion) has been prepared through the simultaneous use of two different anionic ReIV complexes, namely [ReCl4(ox)]2- and [ReCl6]2-, in the presence of MnII ion, the [ReCl6]2- anion playing a key role in the crystallization process. 1 has been magnetically characterized and its crystal structure determined by single-crystal X-ray diffraction. The study of the magnetic properties reveals the occurrence of intramolecular antiferromagnetic exchange between ReIV and MnII ions. Remarkably, 1 is the first reported example of ReIV salt based on two different anionic ReIV complexes.

Anions are ubiquitous in our daily life. Over the past two decades the study of systems based on anions of different nature has seen a remarkable expansion, leading to exciting discoveries, including recent developments in the area of molecular recognition and sensing that have generated a plethora of new selective receptors within the field of supramolecular chemistry.1-12 Anionic species play a key role in very important processes dealing with separation, purification, ion exchange, and crystallization techniques, among others.1-8 Nevertheless, the investigation of a great variety of anions, and their importance for instance in environment, biological systems, medical applications and materials science, still represents a continuous challenge.9-12 Most of the reported inorganic anions employed in anion-based crystal engineering are diamagnetic in nature.11-13 In comparison, the use of paramagnetic anions to that end has been much less explored, despite presenting in many cases a value added and interesting effects in terms of magnetic properties.13 In this respect, double (mixed) salts containing more than one paramagnetic anion (or cation) are particularly attractive, since the magnetic properties of the double salt could not be the same as those of its component single salts. On the one hand, a variety of single salts of mononuclear hexahalo anions of ReIV, of general formula [ReX6]2- (X = F, Cl, Br, I), have been investigated for decades mainly because of their longrange magnetic ordering in the solid state.14-22 Significant intermolecular antiferromagnetic interactions between the paramagnetic and highly anisotropic ReIV metal ions take place in [ReX6]2salts of univalent cations.15-18 The magnetic exchange is mainly transmitted through Re–X⋯X–Re contacts and other weak intermolecular interactions within the crystal lattice.14-22 This magnetic exchange pathway is indeed supported by DFT type calculations, which have showed that the spin density from the metal ion is somewhat delocalized onto the peripheral atoms of its coordinated ligands.15,23

Since in these systems the intermolecular halogen···halogen distance depends on the countercation size, bulky organic cations such as tetraphenylarsonium (AsPh4+) and tetra-n+ butylammonium (NBu4 ) preclude the magnetic exchange between adjacent hexahalorhenate(IV) anions.14-22 However, paramagnetic cations can also provide new insights into the properties of this family of magnetic materials. Indeed, previous studies on [ReCl6]2- salts of organometallic ferrocenium,17 organic radicals,24 and RuIII cations25 revealed the occurrence of other magnetic phenomena, such as ferromagnetism and spin canting.17,24-26 More recently, the use of cationic salicylamidoxime-based [MnIII6]2+ single-molecule magnets (SMMs) as countercations in [ReCl6]2salts has also been explored.27 In these cationic SMMs, the energy barrier to magnetization relaxation is increased just by replacing diamagnetic ClO4- anions with the paramagnetic and highly anisotropic ReIV ion in the form of anionic [ReCl6]2- species.27 In an earlier work, the magnetic properties of a family of heterotetranuclear oxalato-bridged anionic complexes, of general formula (NBu4)4[{ReIVCl4(µ-ox)}3MII] (M = MnII, FeII, CoII, NiII, and CuII), were investigated.28 The NiII derivative was found to exhibit SMM behavior, this complex being the first example of oxalate-based SMM.29 Nevertheless, the crystal structure of the MnII derivative was not reported, given that this compound was obtained as a fine solid and all the attempts to grow X-ray quality crystals were unsuccessful.28

Figure 1. View of the molecular structure of the [ReCl6]2- and [{ReCl4(µ-ox)}3Mn]4- anions of 1. Color code: violet, Re; yellow, Mn; green, Cl; red, O; grey, C [Symmetry code: (a) = 1-x, -y, -z]. Herein we report the synthesis and magnetostructural study of an unusual ReIV-MnII compound of formula (NBu4)10[{ReIVCl4(µox)}3MnII]2[ReIVCl6] (1) [NBu4+ = tetra-n-butylammonium cation and ox2- = oxalate dianion] (Fig. 1). Under the synthetic conditions of 1, the crystallization of the anionic [{ReIVCl4(µox)}3MnII]4- species takes place only when the [ReCl6]2- anion is

ACS Paragon Plus Environment

Crystal Growth & Design

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

added to the reaction mixture. Given that this ReIV-MnII compound is obtained by combination of two different anionic ReIV complexes, namely [ReCl4(ox)]2- and [ReCl6]2-, in the presence of MnII ion, 1 is remarkably the first example of a double salt based on two different anionic ReIV precursors. 1 crystallizes in the monoclinic system with space group P21/c (Tables 1 and S1), and its structure is made up of [ReCl6]2- and [{ReCl4(µ-ox)}3Mn]4- anions together with NBu4+ cations (Figure 2), which are held by electrostatic forces and weak C-H···Cl and C-H···O interactions. The mononuclear [ReCl6]2- anion contains a six-coordinate ReIV ion, bonded to six chloride ions in a regular octahedral geometry (Figure 1, left). No significant differences are seen in the Re-Cl bond lengths [the average value is 2.392(7) Å], which are in agreement with those found in previously reported compounds containing this mononuclear anion.25,26 The star-like tetranuclear [{ReCl4(µ-ox)}3Mn]4- anion contains a central MnII ion and three peripheral ReIV ions, which are bridged through three bisbidentate oxalate ligands in a coplanar arrangement. The values of the Re⋯Mn separation across the bridging oxalate vary in the range 5.546(2)-5.571(2) Å. The three peripheral ReIV ions are surrounded by two oxalate O atoms and four chloride ions each, which form a distorted octahedral geometry (Figure 1, right). The short bite angle of the oxalate group is the main cause of the observed distortion, the value of the angle subtended by this ligand at the ReIV ion being 79.0(4)°. The bond lengths and angles within the [ReCl4(ox)] fragments are in agreement with those found for this complex in previous reports.14,15,28,29 The best equatorial plane around these three ReIV ions is defined by the O(3)-O(4)-Cl(2)-Cl(3) [at Re(1)], O(7)-O(8)-Cl(6)Cl(7) [at Re(2)], and O(10)-O(11)-Cl(10)-Cl(11) [at Re(3)] sets of atoms, with the value of the largest deviation from the mean plane being 0.033(4) Å at O(8) atom. The ReIV ions lie in the respective equatorial planes in 1 with maximum deviation of 0.029(3) Å at Re(1). The values of the dihedral angles between each equatorial plane and the respective oxalate group are 9.8(3) [Re(1)], 6.6(3) [Re(2)] and 4.8(4)° [Re(3)]. The MnII ion is six-coordinate and bonded to six oxalate O atoms from three [ReCl4(ox)]2- units building also a distorted octahedral geometry (Figure 1, right). As observed for the ReIV ion in this anionic unit, the main source of distortion of the ideal octahedral geometry at the MnII ion is the reduced bite angle of the oxalate group [the values of the O(1)-Mn(1)-O(2), O(5)-Mn(1)O(6) and O(9)-Mn(1)-O(12) angles varying in the range 74.6(4)77.1(1)°]. The values of the Mn-O bond lengths in 1 vary in the range 2.172(10)-2.245(10) Å and are close to those observed for other oxalato-bridged ReIV-MnII complexes.30-32 Evaluation of the s/h ratio (s/h = 1.11) and degree of twist of the trischelated environment of the MnII ion (φ = 33°) provides a measure of trigonal distortion in 1 (s/h = 1.22 and φ = 60° for a regular octahedron),33,34 which is quite greater when compared with that of the parent [{ReIVCl4(µ-ox)}3MII]4- complexes [MII (φ) = FeII (60°), CoII (59°), NiII (49°), and CuII (60°)].28 Two of the three oxalate groups are practically planar in 1, while the one connecting Re(2) is remarkably distorted with largest deviation from the mean plane being 0.118(5) Å at O(7). The values of the dihedral angles between their mean planes in each trischelated {MnII(ox)3} fragment cover the range 68.6(3)86.1(3)°. The C-C and C-N bond lengths and angles of the tetra-n-

Page 2 of 6

butylammonium cations in 1 agree with those found in previously reported salts.28-31 The observed scatter in the C-C and N-C distances and in the C-C-C and N-C-C angles doubtless arises from the considerable thermal motion, which is quite a common feature of this cation in most of its compounds.

Figure 2. Perspective view along the crystallographic b axis of a fragment of the crystal packing of 1, showing the arrangement of the [ReCl6]2- and [{ReCl4(µ-ox)}3Mn]4- anions. Bulky organic NBu4+ cations are shown as an orange wireframe model. Color code: violet, Re; yellow, Mn; green, Cl; red, O; grey, C.

In the crystal packing of 1, [ReCl6]2- and [{ReCl4(µ-ox)}3Mn]4anions are well separated due to the bulky tetra-n-butylammonium cations (Figures 2 and S1-S3), as showed by the values of the shortest intermolecular Re···Re [8.965(1) Å for Re(1)···Re(1b), (b) = -x,+y-1/2,-z+1/2] and Cl···Cl [5.088(2) Å for Cl(2)···Cl(3b)] distances.

Figure 3. a) Detail of the weak C-H···Cl interactions (dashed lines) between NBu4+ cations and [ReCl6]2- anions in 1. b) Detail

ACS Paragon Plus Environment

Page 3 of 6

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

of the weak C-H···Cl and C-H···O interactions (dashed lines) between NBu4+ cations and [{ReCl4(µ-ox)}3Mn]4- anions in 1. Color code: violet, Re; yellow, Mn; green, Cl; red, O; blue, N; grey, C; white, H.

lecular antiferromagnetic exchanges between ReIV ions in the crystal lattice.14 However, it seems that the [ReCl6]2- and [{ReCl4(µ-ox)}3Mn]4- anions are too separate each other to generate significant through-space magnetic interactions between the paramagnetic centers.

In fact, the overall packing is characterized by [ReCl6]2- and [{ReCl4(µ-ox)}3Mn]4- anions surrounded by NBu4+ cations. All the halogen atoms of [ReCl6]2- are involved in weak C-H···Cl interactions (Figure 3a) [H···Cl and C···Cl distances covering the ranges 2.755(4)-2.967(4) and 3.459(4)-3.684(4) Å, respectively]. The star-like tetranuclear moieties are also connected through similar C-H···Cl interactions [H···Cl and C···Cl distances varying in the ranges 2.769(4)-2.997(3) and 3.650(4)-3.880(5) Å, respectively] and additional C-H···O interactions [H···O and C···O distances in the ranges 2.495(3)-2.760(4) and 3.439(4)3.599(3) Å, respectively], involving the oxygen atoms of all oxalate bridging groups (Figure 3b). In particular, among these interactions, the ones connecting Cl(13) [Cl(13)···H(79Bc) and C(79c)···Cl(13) with 2.807(2) and 3.763(2) Å, respectively, (c) = -x + 1, +y-1/2,-z+1/2] lead to supramolecular chains, containing [ReCl6]2- and NBu4+ ions, developing along the crystallographic b axis (Figure 4). Figure 5. Plot of the χMT product vs. T for 1. The solid red line represents the best-fit of the experimental data.

Figure 4. View along the crystallographic c axis of the supramolecular one-dimensional motif generated through weak C-H···Cl interactions (dashed lines) between diamagnetic NBu4+ cations and paramagnetic [ReCl6]2- anions in 1. The magnetic properties of 1 in the form of χMT vs. T plot (χM is the magnetic susceptibility per two tetranuclear ReIV3MnII and one mononuclear ReIV units) are given in Figure 5. At room temperature the χMT value is ca. 19.60 cm3 mol−1 K, which is as expected for two MnII (3d5, S = 5/2 with t2g3eg2 configuration) and seven ReIV ions (5d3, S = 3/2 with t2g3 configuration) when magnetically isolated. Upon cooling, the χMT values for 1 decrease, at first slowly and then more abruptly, with decreasing the temperature, reaching a final value of 3.20 cm3 mol−1 K at 2.0 K (Figure 5). The decrease of the χMT values observed for 1 is due to the presence of intramolecular antiferromagnetic interactions and the effect of the zero-field-splitting (zfs), the latter being very important in ReIV compounds.14 No maximum of the magnetic susceptibility is observed in the χM vs. T plot of 1. The field dependence of the molar magnetization (M) plot for 1 at 2.0 K is given in Figure S4, which exhibits continuous increase of M with applied magnetic field. The maximum value of M (ca. 15.4 µB) is consistent with the occurrence of intramolecular antiferromagnetic interactions between the MnII and ReIV ions.14,28 According to the crystal structure of 1, an intramolecular magnetic exchange would be expected between the MnII and ReIV ions through the oxalate bridges in each tetranuclear [{ReCl4(µox)}3Mn]4- unit (Figure 1), as previously observed in other oxalate-bridged ReIV-MnII complexes (Table 1). On the other hand, it is known that short Re-Cl···Cl-Re contacts can transmit intermo-

Taking these facts into consideration, we have used the Hamiltonian of eqn 1 (see Fig. S5), including a term to account for the presence of the isolated [ReCl6]2- anion, in order to analyze the magnetic behavior of 1. In eqn 1, JReMn is the intramolecular magnetic exchange constant between each peripheral ReIV and the central MnII local spins, whereas DMn and DRe are the zfs of the MnII and ReIV ions, respectively. The last term in eqn 1 accounts for the Zeeman effects of the involved metal ions (see Fig. S5).

Figure 6. Schematic showing the main ferro- [(a)-(c)] and antiferromagnetic [(d)-(f)] exchange contributions between pairs of t2g(Re)/eg(Mn) and t2g(Re)/t2g(Mn) magnetic orbitals, respectively, from the ReIV and MnII ions through the σ- and/or π-type orbital pathways of the oxalato bridge in 1.

ACS Paragon Plus Environment

Crystal Growth & Design

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 6

Table 1. Selected magneto-structural parameters for polynuclear oxalate-bridged complexes based on ReIV and MnII Compound

1 (NBu4)4[{ReCl4(µ-ox)}3Mn] (NBu4)2[{ReBr4(µ-ox)}2Mn(Him)2] (NBu4)2[{ReCl4(µ-ox)}2Mn(Him)2] [ReCl4(µ-ox)Mn(dmphen)2]·MeCN

Space Group

d(Re···Mn ) / Åa

d(Mn-O) / Åb

JReMn / cm-1

|DRe| / cm-1

gRe

gMn

Reference

P21/c C2/c C2/c P21/c

5.56(1) 5.62(1) 5.61(1) 5.65(1)

2.20(1) 2.24(1) 2.25(1) 2.30(1)

-1.61 -1.30 -1.10 -0.35 -0.20

48.1 23.1 28.2 35.7 45.0

1.80 1.95 1.90 1.90 1.85

2.00 2.00 2.00 2.00 2.00

This work 28 30 31 32

a Average value of the Re···Mn distance through the bridging oxalate. bAverage value of the Mn-O bond length. Abbreviations: NBu4+ = tetra-nbutylammonium; ox2- = oxalate dianion; Him = imidazole; dmphen = 2,9-dimethyl-1,10-phenanthroline.

In order to reduce the large number of variable parameters and to avoid overparameterization, we have assumed isotropic g values (g// = g⊥) for both metal ions, considered only one unique D value for all ReIV ions, and D = 0 for the MnII ion, as done in previous reports.30,31 Best least-squares fit of the experimental data of 1 through eqn 1 in the 2-300 K temperature range afforded the parameters: JReMn = -1.61 cm-1, gRe = 1.80, gMn = 2.00, |DRe| = 48.10 cm-1, with R = 2.8 x 10-5 {R is the agreement factor defined as Σi[(χMT)obs(i) - (χMT)calc(i)]2 / Σi[(χMT)obs(i)]2}. The theoretical curve (solid red line in Fig. 5) pretty much matches the experimental magnetic data in the studied temperature range. The addition of a θ parameter, considering intermolecular interactions, was neither needed to reproduce the experimental data at low temperature nor improved further the fit, which reveals that such intermolecular interactions are not significant and that the separation between [ReCl6]2- and [{ReCl4(ox)}3Mn]4- anions is ensured well by the organic, bulky tetrabutyl-n-ammonium cations in the crystal lattice of 1. The gMn, gRe and DRe values calculated for 1 are in agreement with those previously reported for other systems involving the same metal centers connected by oxalate (see Table 1).14 The antiferromagnetic exchange observed in 1 (-JReMn = 1.61 cm-1) is somewhat greater than that found in related oxalate-bridged manganese(II)-rhenium(IV) complexes reported in the literature (JReMn = 0.20-1.30 cm-1) (Table 1).28,30-32 The overall antiferromagnetic nature of the magnetic exchange between the MnII (t2g3eg2 electronic configuration) and ReIV (t2g3 electronic configuration) ions, through the σ- and/or π-type orbital pathways of the oxalato bridge (see Fig. 6), indicates that the principal antiferromagnetic contributions between pairs of t2g(Re)/t2g(Mn) magnetic orbitals are stronger than the ferromagnetic ones involving the t2g(Re)/eg(Mn) pairs, as illustrated in Figure 6.35 Only three previous crystal structures of polynuclear oxalatebridged complexes based on ReIV and MnII have been published so far, their associated values of JReMn, intramolecular Re-ox-Mn distances, and Mn-O bond lengths are shown in Table 1. These data suggest that the antiferromagnetic contribution to the overall magnetic exchange JReMn is higher with shortening the Mn-O bond lengths, which is ultimately reflected in the shorter intramolecular Re-ox-Mn distances (see Fig. S6). Nevertheless, additional studies including more systems of this family of complexes will be necessary to establish deeper understanding and magneto-structural correlations.

In summary, a novel rhenium(IV)-manganese(II) compound of formula (NBu4)10[{ReCl4(ox)}3Mn]2[ReCl6] (1) has been prepared through the simultaneous use of the anionic ReIV complexes [ReCl4(ox)]2- and [ReCl6]2- in the presence of MnII ion. 1 is the first reported example of double salt based on two different anionic ReIV complexes. The magnetic properties have also been investigated, showing that 1 exhibits the strongest antiferromagnetic exchange reported for polynuclear oxalate-bridged complexes based on ReIV and MnII. This study suggests that the magnetic exchange should be more antiferromagnetic with decreasing the Mn-O bond lengths and the intramolecular Re-ox-Mn distance. Finally, given that the [ReCl6]2- anion is employed as a crystallization agent in the synthesis of 1, we have reported here an original synthetic route to generate new ReIV compounds which, in some scenarios,36 could display versatile structures and multiple properties.

Supporting Information Preparation of 1, Table S1, and Figures S1-S6. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *(D.A.) E-mail: [email protected] *(J.M.-L.) E-mail: [email protected]

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT Financial support from the Italian Ministero dell'Istruzione, dell'Università e della Ricerca Scientifica (MIUR), the Spanish Ministry of Economy and Finance (MINECO) (project CTQ201344844P) and the Excellence Unit “Marı́a de Maeztu” (project MDM-2015-0538) is gratefully acknowledged. JML thanks the Spanish MINECO for a “Ramón y Cajal” grant. The authors wish to thank Prof. G. De Munno, Prof. J. Faus, Prof. E. K. Brechin, Prof. F. Lloret and Prof. M. Julve for their constant and valuable encouragement.

REFERENCES (1) (2) (3) (4)

Lehn, J.-M. Supramolecular Chemistry, Wiley-VCH, 1995. Moyer, B. A.; Singh, R. P. Fundamentals and Applications of Anion Separations, Springer, 2004. Chifotides, H. T.; Schottel, B. L.; Dunbar, K. R. Angew. Chem. Int. Ed. 2010, 49, 7202-7207. Gale, P. A.; Dehaen, W. Anion Recognition in Supramolecular Chemistry, Springer, 2011.

ACS Paragon Plus Environment

Page 5 of 6

Crystal Growth & Design (5)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36)

Frontera, A.; Gamez, P.; Mascal, M.; Mooibroek, T. J.; Reedijk, J. Angew. Chem., Int. Ed. 2011, 50, 9564-9583. Frontera, A. Coord. Chem. Rev. 2013, 257, 1716-1727. Caballero, A.; Zapata, F.; Beer, P. D. Coord. Chem. Rev. 2013, 257, 2434-2455. Evans, N. H.; Beer, P. D. Angew. Chem., Int. Ed. 2014, 53, 11716-11754. Bianchi, A.; Bowman-James, K.; García-España, E. Supramolecular Chemistry of Anions, Wiley-VCH, Germany, 1997. Bowman-James, K.; Bianchi, A.; García-España, E. Anion Coordination Chemistry, Wiley-VCH, Germany, 2012. Gale, P. A.; Gunnlaugsson, T. Chem. Soc. Rev., 2010, 39, 3595-3596. Custelcean, R. Chem. Soc. Rev. 2010, 39, 3675-3685. Braga, D.; Grepioni, F.; Orpen, A. G. Crystal Engineering: From Molecules and Crystals to Materials, Springer, 1999. Martínez-Lillo, J.; Faus, J.; Lloret, F.; Julve, M. Coord. Chem. Rev. 2015, 289–290, 215-237. Chiozzone, R.; González, R.; Kremer, C.; De Munno, G.; J. Cano, J.; Lloret, F.; Julve, M.; Faus, J. Inorg. Chem. 1999, 38, 4745-4752. González, R.; Chiozzone, R.; Kremer, C.; De Munno, G.; Nicolò, F.; Lloret, F.; Julve, M.; Faus, J. Inorg. Chem. 2003, 42, 2512-2518. González, R.; Chiozzone, R.; Kremer, C.; Guerra, F.; De Munno, G.; Lloret, F.; Julve, M.; Faus, J. Inorg. Chem. 2004, 43, 3013-3019. Martínez-Lillo, J.; Armentano, D.; De Munno, G.; Lloret, F.; Julve, M.; Faus, J. Cryst. Growth Des. 2006, 6, 2204-2206. Martínez-Lillo, J.; Kong, J.; Julve, M.; Brechin, E. K. Cryst. Growth Des. 2014, 14, 5985-5990. Martínez-Lillo, J. Polyhedron 2014, 67, 213-217. Martínez-Lillo, J.; Julve, M.; Brechin, E. K. Polyhedron 2015, 98, 35-39. Martínez-Lillo, J.; Pedersen, A. H.; Faus, J.; Julve, M.; Brechin, E. K. Cryst. Growth Des. 2015, 15, 2598-2601. Cuevas, A.; Chiozzone, R.; Kremer, C.; Suescun, L.; Mombrú, A.; Armentano, D.; De Munno, G.; Lloret, F.; Cano, J.; Faus, J. Inorg. Chem. 2004, 43, 7823-7831. González, R.; Romero, F.; Luneau, D.; Armentano, D.; De Munno, G.; Kremer, C.; Lloret, F.; Julve, M.; Faus, J. Inorg. Chim. Acta 2005, 358, 3995-4002. Armentano, D; Martínez-Lillo, J. Inorg. Chim. Acta 2012, 380, 118-124. Martínez-Lillo, J.; Armentano, D.; De Munno, G.; Marino, N.; Lloret, F.; Julve, M.; Faus, J. CrystEngComm 2008, 10, 12841287. Martínez-Lillo, J.; Cano, J.; Wernsdorfer, W.; Brechin, E. K. Chem. Eur. J. 2015, 21, 8790-8798. Martínez-Lillo, J.; Armentano, D.; De Munno, G.; Wernsdorfer, W.; Clemente-Juan, J. M.; Krzystek, J.; Lloret, F.; Julve, M.; Faus, J. Inorg. Chem. 2009, 48, 3027-3038. Martínez-Lillo, J.; Armentano, D.; De Munno, G.; Wernsdorfer, W.; Julve, M.; Lloret, F.; Faus, J. J. Am. Chem. Soc. 2006, 128, 14218-14219. Martínez-Lillo, J.; Mastropietro, T. F.; De Munno, G.; Lloret, F.; Julve, M.; Faus, J. Inorg. Chem. 2011, 50, 5731-5739. Martínez-Lillo, J.; Delgado, F. S.; Ruiz-Pérez, C.; Lloret, F.; Julve, M.; Faus, J. Inorg. Chem. 2007, 46, 3523-3530. Chiozzone, R.; González, R.; Kremer, C.; De Munno, G.; Armentano, D.; Lloret, F.; Faus, J. Inorg. Chem. 2003, 42, 10641069. Kepert, D. L. Prog. Inorg. Chem. 1977, 23, 1-65. Stiefel, E. I.; Brown, G. F. Inorg. Chem. 1972, 11, 434-436. Vallejo, J.; Castro, I.; Cañadillas-Delgado, L.; Ruiz-Pérez, C.; Ferrando-Soria, J.; Ruiz-García, R.; Cano, J.; Lloret, F.; Julve, M. Dalton Trans. 2010, 39, 2350-2358. Martínez-Lillo, J.; Armentano, D.; Fortea-Pérez, F. R.; Stiriba, S.-E.; De Munno, G.; Lloret, F.; Julve, M.; Faus, J. Inorg. Chem. 2015, 54, 4594-4596.

5

ACS Paragon Plus Environment

Crystal Growth & Design

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 6

For Table of Contents Use Only:

Anion-assisted crystallization of a novel type of rhenium(IV)based salt Donatella Armentano* and José Martínez-Lillo*

A novel rhenium(IV)-manganese(II) compound of formula (NBu4)10[{ReCl4(ox)}3Mn]2[ReCl6] (1) (NBu4+ = tetra-nbutylammonium cation and ox2- = oxalate dianion) has been prepared through the simultaneous use of the anionic ReIV complexes [ReCl4(ox)]2- and [ReCl6]2- in the presence of MnII ion, the [ReCl6]2- anion playing a key role in the crystallization process.

6

ACS Paragon Plus Environment