Self-Organization into Preferred Sites by MgII, MnII, and MnIII in

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

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Self-Organization into Preferred Sites by MgII, MnII, and MnIII in Brucite-Structured M19 Cluster Bao-Qian Ji,†,⊥ Hai-Feng Su,‡,⊥ Marko Jagodic,̌ #,⊥ Zvonko Jaglicǐ c,́ *,# Mohamedally Kurmoo,*,§ Xing-Po Wang,*,† Chen-Ho Tung,† Zao-Zhen Cao,*,† and Di Sun*,†,‡

Inorg. Chem. Downloaded from pubs.acs.org by WEBSTER UNIV on 03/01/19. For personal use only.

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Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan, 250100, People’s Republic of China ‡ State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China # Faculty of Civil and Geodetic Engineering & Institute of Mathematics, Physics and Mechanics, University of Ljubljana, Jamova 2, 1000 Ljubljana, Slovenia § Institut de Chimie de Strasbourg, Université de Strasbourg, CNRS-UMR 7177, 4 rue Blaise Pascal, 67008 Strasbourg Cedex, France S Supporting Information *

ABSTRACT: The search for functional materials, for example those aiming at microelectronics, magnetic recording, and catalysis, often ventures into mixed metal systems to achieve optimization of the properties. Thus, understanding site preference and self-organization is crucial but hard to implement. Herein, we present a system whereby MgII, MnII, and MnIII ions selectively locate exact positions within the Brucitestructured cluster, Mn13Mg6, [MnIII⊂MgII6⊂MnII9MnIII3(L)18(OH)12(N3)6](ClO4)6· 12CH3CN, HL = 1-(hydroxymethyl)-3,5-dimethylpyrazolate). The MnIII being small (78 pm) takes up the core position; while 6 MgII (86 pm) are located in the inner ring, and the 9 large MnII (97 pm) and 3 MnIII occupy the outer ring. The factors (a) ionic radii, (b) regularity in coordination geometry, oxophilicity, and softness of MgII compared to MnII, and (c) Jahn−Teller distortion of MnIII may all be implicated synergistically. Electrospray ionization mass spectrometry reveals the M19 disc remains an integral unit when crystals are dissolved, and exchange between Mg and Mn occurs within the disc during its formation. Diamagnetic MgII doping insulates the magnetic exchange between the central MnIII and those in the outer ring, thus giving an overall antiferromagnetic exchange interaction between nearest-neighbors of the outer ring. The work reveals the underlying rule for site-preference of main group metal versus transition metal in disc-like Brucite-structured cluster and provides an elegant new avenue to assemble heterometallic clusters in a stepwise fashion.

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INTRODUCTION Miniaturization requirements for microelectronics and magnetic recording applications are the driving force behind numerous designs at the molecular level.1 One approach, top to bottom, is to fragment existing infinite structures into small segments that still retain the properties of the bulk materials.2 This is more so for magnetic materials where the nanosized particles retain the magnetism and the magnetic pole direction.3 While these are successful, other demands come into play, for example how to reduce the dipolar field in an array of these particles. With nanoparticles of magnetic metals or metal oxides, this is done by casting them in silica or some diamagnetic organic polymers.4 In contrast, high-nuclearity clusters of paramagnetic metal ions is becoming an important field of research to replace the currently used metal oxides.5 This is so for several reasons, for example (a) the size is controllable and uniform, and (b) their organization on a surface is very regular and the disposition of the ligands around them can be served as a way to eliminate the dipolar fields. Among them, those with a layered structure, like that adopted © XXXX American Chemical Society

by Brucite segments, are becoming prominent in this approach. Brucite is the parent natural mineral Mg(OH)2,6 comprised of octahedral Mg edge-sharing through bridging μ3-OH to form layers. Several other metals with hydroxide, oxide, chacogenides, and halides adopt this structure. Numerous small fragmented Brucite-structured coordination clusters are reported for Mn7, Fe7, Ni7, Co7, Mn15, Mn24Ni2 Fe13, and Fe19,7,8 while the genuine MgII-containing Brucite clusters are still rare; only two Mg7 clusters are known.9 Thus, larger Mgbased Brucite clusters remain a challenge. Hierarchical polynuclear metal clusters invariably form via secondary structures governed by kinetics and thermodynamics. Thus, a range of intermediates can be formed during the assembly process. However, several considerations are needed, viz: coordination preference, ionic radii, charge, and solubility products. Importantly, the hierarchical formation may progress along different energetically favorable routes Received: December 6, 2018

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DOI: 10.1021/acs.inorgchem.8b03406 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry instead of adopting a random one.10 Our aims are to force the formation along a unique route so that only one final product forms. Thus, due to the stepwise growth, it is also a major decision as to when the dopant is to be added. On the other hand, the N,O-donor chelating ligands such as pyridinealcohols not only assemble heterometallic clusters via the different coordination preferences of N and O but also have additional influence on the assembly due to charges, neutral N, and negatively charged O sites.11 Alternatively, the small fivemembered heterocyclic ligands with alkanol arms such as 1(hydroxymethyl)-3,5-dimethylpyrazole (HL)12 caught our attention recently through the observation of the largest symmetric Brucite-structured Mn19 cluster, [MnII15MnIII4(L)18(OH)12(N3)6](ClO4)6·12CH3CN (Mn19). It comprises a central MnIII in the core, surrounded by 6 MnII/III in the inner ring and 12 MnII in the outer ring (Scheme 1). It behaves as a weak ferromagnet due to the existing dipolar

position in tuning the physicochemical properties from those of the homometallic counterparts.14 Although it remains a real challenge, some advances in the synthesis have recently been made,15 such as the use of metalloligands in a two-step assembly fashion.16 Exchange or doping are other promising strategies to assemble heterometallic clusters and modulate their properties, while the basic backbone of metal cluster is maintained. However, two questions pose: (a) where does the doping metal ion go, and (b) how many are inserted into the pristine cluster? Answers are not easy as these problems are very hard to control, and the rules do not follow those applied to alloy compounds.17

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RESULTS AND DISCUSSION Synthesis. Briefly, the Mn(ClO4)2·6H2O, NaN3, Et3N and HL were reacted in CH3CN for 2−5 min to form a brown turbid solution under the ultrasound condition. After adding solid Mg(NO3)2, this mixture was further reacted under the same condition for another 5−8 min. From the filtrate, yellow block crystals were formed after slow evaporation at ambient temperature for one week. The timing for the introduction of Mg(NO3)2 is less crucial for the synthesis of Mn13Mg6. The energy dispersive X-ray (EDX) mapping for Mn and Mg verified they are regularly dispersed in the crystals (Figure S1). Furthermore, elemental analyses using ICP-AES on these crystals found a Mg:Mn atomic ratio of 6.0:13.2, compared to an expected ratio of 6:13 refined from crystallographic data. Structure of [MnIII⊂MgII6⊂MnII9MnIII3(L)18(OH)12(N3)6] (ClO 4 ) 6 ·12CH 3 CN (Mn 13 Mg 6 ). SCXRD revealed that Mn13Mg6 crystallized in the trigonal R3̅ space group (Table S1) similar to those of Mn19 and Mn13Cd6. Its asymmetric unit contains four metal sites that are assigned to one Mg and three Mn atoms based on the crystallographic Ueq values. Thus, the core, inner, and outer rings are comprised of 1 Mn, 6 Mg and 12 Mn atoms, respectively. The connectivity between the core and the inner ring are 6 μ3-OH− bridges, while those between the inner and outer rings are 6 μ3-OH− and 12 μ3-O phenoxide from the ligands. The remaining 6 μ2-L− and 6 end-on μ2-N3− bridge the Mn of the outer ring. Both Mg and Mn atoms are located in the octahedral coordination geometry with the Mg− O, Mn−O, and Mn−N bond lengths in the ranges of 2.058− 2.139, 2.023−2.261, and 2.186−2.250 Å, respectively. Considering the charge neutrality, all six Mg atoms are +2 (VMg = 1.617 based on bond valence sum calculations);18 the Mn (Mn2) in the center core is +3 (VMn = 2.792), whereas the remaining 12 outer atoms consist of 9 MnII and 3 MnIII which are almost indistinguishable due to the averaged Mn−O/N bond length in this high-symmetry cluster, similar to the observations in both Mn19 and Mn13Cd6 as well as some minerals.19 In the R3̅ trigonal symmetry, the Jahn−Teller distortion is manifested as a compression or elongation of the octahedron along the unique C3-symmetry axis (crystallographic c-axis); thus, the O−MnIII−O angles are symmetrically deviated from the 90° of a regular octahedron. In the present case, there is a compression, and the angles are 83° and 97°.20 The compression of the octahedron is also clearly seen from the O···O distances, being 3.030 Å for the two faces perpendicular to the c-axis and 2.682 Å for the others. The overall geometry of Mn13Mg6 looks like a calix, and two of them sandwiched six ClO4− by O−H···Operchlorate H-bonds (2.90 and 3.00 Å, Figures 1b and 1c). Different organization from the metal site preference of Mn13Cd6, Mn13Mg6 is formed with MgII exclusively in the

Scheme 1. Definition of the Rings and Different Metal Organizations for CdII and MgII in Brucite-Structured M19 Clusters

field within the discotic packing of the structure. Because electrospray ionization mass spectrometry (ESI-MS) reveals the formation is progressive following the stabilization of the small Mn7 cluster, we exploited this behavior in an attempt to continue the synthesis with nonmagnetic CdII doping in the outer ring and successfully obtained the partially exchanged materials, [Cd II 6 Mn II 9 Mn III 4 (L) 18 (OH) 12 (N 3 ) 6 ](ClO 4 ) 6 · 12CH3CN (Mn13Cd6), where 50% of the Mn in the outer ring was replaced by CdII.7 It turns out to be a paramagnet. On the basis of the above considerations, we dope Mn19 with small Mg II (86 pm), preferring a more regular octahedral coordination compared to large CdII (109 pm) without coordination geometry preferences. 13 Surprisingly, MgII replaces all 6 Mn of the inner rings of the Mn19 without any disorder to give Mn13Mg6 [MnIII⊂MgII6⊂MnII9MnIII3(L)18(OH)12(N3)6](ClO4)6·12CH3CN (Scheme 1). The single-crystal X-ray diffraction (SCXRD), ESI-MS of the dissolved crystals, and the reaction mother liquor at different times during the synthesis, elemental mapping, and ICP-AES verified the successful doping. This study reveals that alkaline earth group IIA oxophilic Mg ion prefers the more regular octahedral site. The crystallography confirms a clear dependence on ionic size, where the small MnIII takes the core position, followed by 6 MgII in the inner ring and 12 MnII/III in the outer ring. ESI-MS results show that Mg clusters are formed first and then Mg is progressively replaced by Mn, presumably in the outer ring, leading to the crystallization of the titled compound. The result is a long-sought target in coordination chemistry with regard to varying the metal class, ratio, and relative B

DOI: 10.1021/acs.inorgchem.8b03406 Inorg. Chem. XXXX, XXX, XXX−XXX

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are coordinated to oxygen atoms and Mg−O bond lengths are 2.093 Å.6 Regarding this, the best doping sites of MgII in Mn19 cluster are in the inner ring where all metal atoms are in regular MO6 octahedron. The coordination environment of the metals in the outer ring is octahedral MO4N2, which is highly distorted due to the longer M−N bond length. Consequently, the two different crystallographic metal sites in the outer ring are not preferred by MgII. Moreover, the central Mn atom is +3, which is small compared to MgII and occupies the core. On the other hand, the ionic radii of MgII (86 pm) is small compared to CdII (109 pm) and MnII (high-spin, 97 pm), but larger than MnIII (high-spin, 78.5 pm);13 thus, MgII ions have a faster kinetics than MnII during the assembly process. Although Mn7 intermediate can be formed within the initial 1−2 min during the assembly of Mn19 cluster, MgII ions can easily occupy the outer ring of Mn7 due to its favorable kinetics. On the basis of the above considerations, it is possible to envisage the unique site selectivity of MgII in the Mn13Mg6 cluster. Comparing the structures and contents of the three compounds Mn19, Mn13Cd6, and Mn13Mg6, it appears that the packing efficiency is optimized for 6 perchlorate anions and 12 acetonitrile solvents. Thus, the complexes are all 6+, implying that whatever the starting mixture is, the final products are forced to balance the charge, which is driven by the packing and possibly the supramolecular interactions. Interestingly, as found in the present study, it appears several charge distributions are possible, which depend on the factors listed earlier. It would be interesting to see what will be the structures and distributions that will be obtained if one mixes trivalent ions (Cr, Fe, Ga, Al, In, Ir, etc.) in the preparations. Electrospray Ionization Mass Spectrometry. Crystals of Mn13Mg6 were dissolved in CH3CN using an ultrasonic bath before collecting ESI-MS data at 200 °C. As shown in Figure 2, there are two regions containing the MnxMgy species (x:y = 13:6 or 14:5). In the range of m/z = 1100−1300, there are three strong triply charged species (1A, 1B, and 1C) which are severely overlapped and comprise of two species for each

Figure 1. (a) A photo of the crystals of Mn13Mg6 taken under the microscope showing their regular shape and size. Structure of Mn13Mg6 (b) viewed along the c-axis (50% probability ellipsoids), (c) and (d) side and top views showing two molecules trapping the Hbonded (black dashed lines) perchlorate. Color code: Mn purple, Mg cyan, N blue, O red, C gray, Cl, green.

inner ring. This is related to several characteristics of MgII: (i) oxophilicity, (ii) coordination preference, (iii) regularity, and (iv) ionic radii. Due to the similar doping synthesis process, MgII was expected to locate in the second ring like CdII. However, it indeed behaves different from CdII. The Mg is sblock, while Cd is d-block metal, so when they are located in octahedral coordination, the former prefers more regular geometry like in real Brucite mineral where all the Mg atoms

Figure 2. Positive mode ESI mass spectrum of Mn13Mg6 dissolved in acetonitrile. Insets: Enlarged section showing the +3 {Mn13Mg6} (green ball) and +2 {Mn13Mg6} (green ball) and {Mn14Mg5} (purple ball) species family (black line represents experimental data, red line represents simulated ones). C

DOI: 10.1021/acs.inorgchem.8b03406 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry envelope. A total of six species in this region were identified based on isotope mass distribution patterns, and their formulas are listed in Table S2. All of them retain a complete Mn13Mg6 skeleton, but the ligands exchange between N3− and OH− was observed to some extent. The m/z = 1750−1900 region is dominated by five doubly charged species (1D, 1E, 1F, 1G, and 1H) with severe overlapping of the peaks. From 1D to 1G, each peak contains 3, 4, 4, 4, and 2 species, respectively, and a total of 17 species were assigned with precise formulas. Taking 1D as an example, it contains three species, 1d, 1d′, and 1d″, which are assigned to Mn13Mg6(L)16(N3)1(OH)8(H2O)3, Mn14Mg5(L)16(N3)12(OH)10(H2O)2, and Mn13Mg6(L)16(N3)12(OH)12(H2O)2, respectively (Table S2). These formulas indicate that both metal ion and anion exchanges occur in these species. Similar phenomenon was also observed for species in 1E and 1F. Based on the above analyses, we found (i) all the species maintain the integrity of 19-metal disc in CH3CN; (ii) both metal ion and ligand exchange is a universal phenomenon; and (iii) no species with more than six Mg ions are found in solution, indicating the doping of MnII ions in this system may be strictly confined in the inner ring. Furthermore, we also collected the ESI-MS of the reaction mother liquor before and after adding Mg(NO3)2. Before adding Mg(NO3)2, we observe a series of Mn cluster intermediates such as Mn7, Mn10, and Mn12 (Figure S2a), which are similar to those observed in time-course ESI-MS of Mn19.12 Once adding Mg(NO3)2 to the above solution, some Mg substituted Mn cluster intermediates like MgMn11 and Mg6Mn12 (Figure S2b) appeared in the ESI-MS. The formulas of these intermediates were assigned based on comparison of simulated and experimental isotope distributions (Figure S3) and listed in the inserted table in Table S4. These results indicate the exchange and/or substitution between Mg and Mn occurs within the disc during its formation. Magnetic Properties. The magnetic properties of Mg6Mn13 were studied with a Quantum Design MPMS XL-5 SQUID magnetometer. The zero field-cooled (ZFC) and the field-cooled (FC) magnetic susceptibilities were measured between 2 and 300 K in a field of 1 kOe. The magnetic field dependence of the magnetization was investigated at 2 K in a magnetic field between −50 to +50 kOe. The acsusceptibilities were investigated in a magnetic field oscillating at frequencies of 1, 10, 100, and 1000 Hz between 2 and 20 K. The data were corrected for the contribution of the sample holder and the diamagnetic contribution.21 The temperature dependence of the magnetic susceptibility exhibits Curie−Weiss like behavior with no splitting between the ZFC an FC curve (Figure 3). The product χT has a constant value of 58 emu K/mol above 100 K and decreases below that temperature (left inset in Figure 3), suggesting antiferromagnetic interactions between magnetic centers in the molecule. The measured data above 100 K are well-described by the Curie−Weiss model χ = C/(T − θ), where C is the Curie constant = 58 emu K/mol and θ the Weiss temperature = −3.5 K (Figure 3). A low negative θ value supports weak antiferromagnetic interactions between Mn ions of the outer ring assuming the exchange between the moment of the core to those on the outer ring is negligible. The Curie constant is slightly larger than the expected 52 emu K/mol for 9 MnII (S = 5 /2) and 3 MnIII (S = 2) assuming g = 2 in each case.22 Given the high spins (S = 5/2 and 2) and the large number of carriers, it is not easy to compute the susceptibility using

Figure 3. Temperature dependence of the magnetic susceptibility measured in an external magnetic field of H = 1000 Oe. The ZFC curve (empty circles) and FC curve (empty squares) coincide. Curie− Weiss fit is shown as a red line. The left inset shows the temperature dependence of the product χT; the error bar is shown for the point at room temperature and corresponds to a 10% uncertainty in the mass of the sample. The right inset shows the magnetization curve, measured at 2 K.

analytical methods. Furthermore, the featureless dependence of the susceptibility on temperature is not favorable for accurate determination of the exchange interactions. Using two very approximate models, a very rough estimate is obtained. The first considers the outer ring as a uniform chain of 12 MnII and applying the Fisher equation for classical spins together with an independent MnIII for the central core.21 Such a model with a Landé g-factor fixed to 2 gives J = −0.63 cm−1 (green full line on left inset of Figure 3). The second model being more realistic is fragmenting the ring into three equal parts that satisfies the symmetry. It assumes a repeating 4 sites ring, MnII−MnII−MnII−MnIII, and two exchange interactions and one g-value. Fitting using the PHI software gives J(MnII−MnII) = −0.18 cm−1, J(MnII−MnIII) = −0.62 cm−1, and g = 2.2 (red dashed line on left inset of Figure 3).23 The g-factor for MnII ions is expected to be 2.0.24,25 The difference is derived from the limiting accuracy in weighing of the small mass sample of only 3.3 mg. The estimated error is 10%. Fitting an adjusted data set does not alter the exchange parameters. The magnetic field dependence of the magnetization is shown in the right inset of Figure 3, and it is a smooth increase to 38 μβ at 50 kOe. This value falls short of the 56 μβ expected for a paramagnet of 9 MnII and 4 MnIII and is associated with the antiferromagnetic coupling between nearest neighbors. The in-phase ac susceptibility gradually increases with decreasing temperature, showing no special feature and no difference between the data measured at different frequencies (Figure S4). Therefore, there is no single-molecule magnetism above 2 K. An important comparison can be made here with reference to Mn19 and Mn13Cd6. Mn19 has the highest moment per cluster of the three and thus a strong dipolar interaction with its neighbors. Consequently, it exhibits long-range ordering. In contrast, for Mn13Cd6, the moment is reduced, and its periphery is diluted by the nonmagnetic CdII which resulted in weak interaction between its neighbors within the crystal. The same is experienced for Mn13Mg6; but this time, the D

DOI: 10.1021/acs.inorgchem.8b03406 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry periphery is all magnetic moments of MnII and MnIII, but still the reduced moment led to no dipolar interaction.

21701133, and 21827801), the bilateral PR China-Slovenian project (Grant BI-CN/17-18-004), the Slovenian Research Agency (Grant P2-0348), the Natural Science Foundation of Shandong Province (Grants JQ201803 and ZR2017MB061), the Taishan Scholar Project of Shandong Province of China, the Qilu Youth Scholar Funding of Shandong University, and the Fundamental Research Funds of Shandong University (Grant 104.205.2.5). M.K. is funded by the CNRS-France.

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CONCLUSIONS In summary, we found that the metrics and coordination preferences decide the positions of MgII, MnII, and MnIII during the synthesis of mixed-metal Brucite Mn13Mg6 cluster. Small MnIII favors the core site followed by medium MgII in the inner ring and a mixture of large MnII and small MnIII on the outer ring. The exact precision in location is also driven by the oxophilic nature of MgII (s-block metal) and thus preferred the MgO6 site of the inner ring compared to Mn, which is easily distorted (MnO4N2) and occupies the outer ring sites. Compared to the CdII doped Mn19 cluster, such unique organization is rarely found. The ESI-MS shows the 19metallic disc retains its integrity, and metal ion exchange occurs within the disc in solution. Diamagnetic MgII doping shields the magnetic exchange between the central MnIII and the MnII and MnIII of the outer ring. Simulation of the magnetic susceptibility gives an average antiferromagnetic exchange between Mn of the outer ring of Mn13Mg6. The work reveals the underlying rule of atom-precise main group metal ion doping in a disc-like Mn19 Brucite cluster and provides a new avenue to synthesize heterometallic clusters in a stepwise fashion.

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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.8b03406. Detailed synthesis procedure; IR, TGA, UV−vis, EPR, CV, and EDS mapping results, and powder X-ray diffractogram (PDF) Accession Codes

CCDC 1879640 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by emailing data_ [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 Authors

*E-mail: *E-mail: *E-mail: *E-mail: *E-mail:

REFERENCES

[email protected]. [email protected]. [email protected]. [email protected]. [email protected].

ORCID

Mohamedally Kurmoo: 0000-0002-5205-8410 Chen-Ho Tung: 0000-0001-9999-9755 Di Sun: 0000-0001-5966-1207 Author Contributions ⊥

B.-Q.J., H.-F.S., and M.J. contributed equally to this work.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (Grants 21822107, 21571115, E

DOI: 10.1021/acs.inorgchem.8b03406 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.8b03406 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.8b03406 Inorg. Chem. XXXX, XXX, XXX−XXX