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Unformatted text preview: ARTICLE pubs.acs.org/IC Synthetic Entry into Polynuclear BismuthÀManganese Chemistry: High Oxidation State BiIII2MnIV6 and BiIIIMnIII10 Complexes Theocharis C. Stamatatos, Katie Oliver, Khalil A. Abboud, and George Christou* Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, United States S b Supporting Information ABSTRACT: The first high nuclearity, mixed-metal BiIII/MnIV and BiIII/MnIII complexes are reported. The former complexes are [Bi2MnIV6O9(O2CEt)9(HO2CEt)(NO3)3] (1) and [Bi2MnIV6O9(O2CPh)9(HO2CPh)(NO3)3] (2) and were obtained from the comproportionation reaction between Mn(O2CR)2 and MnO4À in a 10:3 ratio in the presence of Bi(NO3)3 (3 equiv) in either a H2O/EtCO2H (1) or MeCN/PhCO2H (2) solvent medium. The same reaction that gives 2, but with Bi(O2CMe)3 and MeNO2 in place of Bi(NO3)3 and MeCN, gave the lower oxidation state product [BiMnIII10O8(O2CPh)17(HO2CPh)(H2O)] (3). Complexes 1 and 2 are near-isostructural and possess an unusual and high symmetry core topology consisting of a MnIV6 wheel with two central BiIII atoms capping the wheel on each side. In contrast, the [BiMnIII10O8]17þ core of 3 is low symmetry, comprising a [BiMn3(μ3-O)2]8þ butterfly unit, four [BiMn3(μ4-O)]10þ tetrahedra, and two [BiMn2(μ3-O)]7þ triangles all fused together by sharing common Mn and Bi vertices. Variable-temperature, solidstate dc and ac magnetization data on 1À3 in the 1.8À300 K range revealed that 1 and 2 possess an S = 0 ground state spin, whereas 3 possesses an S = 2 ground state. The work offers the possibility of access to molecular analogs of the multifunctional Bi/Mn/O solids that are of such great interest in materials science. ’ INTRODUCTION Both discrete and polymeric oxide-bridged compounds of Mn or Bi are of relevance to a large number of areas and applications spanning inorganic, biological, materials, and industrial chemistry, as well as to the multidisciplinary fields of magnetism and electronics.1 In a biological context, for example, a high oxidation state Mn4Ca cluster within the photosynthetic apparatus of plants and cyanobacteria is the oxygen-evolving complex (OEC) that catalyzes the oxidation of H2O to O2 and is thus the source of essentially all this gas on the planet.2 This has stimulated extensive efforts to prepare structural and functional model compounds of the OEC, and a large number of Mn4 molecular complexes have been obtained as a result.3 Similarly, polyoxidobismuth species play an important role as pharmaceuticals owing to their relatively low toxicity compared with related species containing other heavy metals such as Hg, Cd, Sn, or Pd,4 and this has stimulated the synthesis of {BixOy} clusters that mimic on a molecular basis the biological properties of the amorphous, polymeric bismuth oxides.5 In the magnetism arena, one area of molecular manganese chemistry that has attracted much attention is that of high-spin molecules and singlemolecule magnets, both arising from the fact that MnIII-containing clusters often possess large, and sometimes abnormally large, ground-state spin (S) values.6 When this is combined with a large and negative magnetoanisotropy (as reflected in a large and negative zero-field splitting parameter, D), single-molecule magnets (SMMs) result,7,8 which represent a molecular approach to nanoscale magnetic materials. In addition, they display quantum r 2011 American Chemical Society effects such as quantum tunneling of the magnetization9 and quantum phase interference,10 offering the potential for use in molecule-based information storage and molecular spintronics,11 as well as quantum information processing.12 In contrast, Bi compounds are diamagnetic, and the areas of greatest potential are thus not magnetism but, for example, applications of nanoparticles of Bi2O3 within sensors and solid electrolytes.13 However, much more technologically important is the broad spectrum of potential applications offered by the variety of heterometallic Bi-containing metal oxides, which have impacted many areas such as sensors, oxidation catalysts, superconductors, photocatalysts, and next-generation data storage materials.14 A field of great importance is the class of mixed-metal oxide multiferroics,15 which are materials simultaneously showing ferromagnetic, ferroelectric, and/or ferroelastic long-range ordering. For example, coupling between the ferroelectric and the magnetic order parameters can lead to intriguing magnetoelectrical effects. Bismuth-containing oxides such as BiMnO3 with a perovskite structure and BiMn2O5 have been the focus of recent attention due to their potential to act as multiferroic materials exhibiting mutually ferromagnetism and ferroelectricity, thus leading to exciting multifunctional materials.15,16 Given the above, it is perhaps surprising that there has been no development of BiIII/MnIII, BiIII/MnIV, and/or BiIII/MnIII/IV molecular cluster chemistry, only a trinuclear BiIII2MnII complex Received: March 30, 2011 Published: April 26, 2011 5272 dx.doi.org/10.1021/ic200656q | Inorg. Chem. 2011, 50, 5272–5282 Inorganic Chemistry having been reported.17 Diamagnetic BiIII obviously brings no magnetic advantage, and Bi/Mn chemistry has therefore not attracted interest, in contrast to the spin and anisotropy considerations that have made mixed Ln/Mn (Ln = lanthanide) compounds so attractive to many groups during the past several years.18 Nevertheless, the mixed-metal oxides made us believe that oxide-bridged Bi/Mn molecular species might exhibit interesting new structures related to those of the mixed-metal oxides, and/or properties distinct from those of homometallic Mn or heterometallic Ln/Mn clusters. We have therefore initiated a new program seeking the development of synthetic methods to Bi/Mn molecular species, and we now report the first compounds from this work. We herein describe the synthesis and crystallographic and magnetic characterization of BiIII2MnIV6 and BiIIIMnIII10 clusters. They are the first high-nuclearity, heteronuclear Bi/Mn complexes of any type and have been prepared by a comproportionation route under acidic conditions in the presence of carboxylate ligands, which are widely employed ligand types in both Mn and Bi homometallic cluster chemistry.19 ’ EXPERIMENTAL SECTION Syntheses. All manipulations were performed under aerobic conditions using chemicals and solvents as received, unless otherwise stated. Mn(O2CEt)2 3 xH2O,20 Mn(O2CPh)2 3 2H2O,21 and NnBu4MnO422 were prepared as described elsewhere. Warning! Appropriate care should be taken in the use of NnBu4MnO4, and readers are referred to the detailed warning given elsewhere.22 [Bi2Mn6O9(O2CEt)9(HO2CEt)(NO3)3] (1). To a stirred colorless solution of Mn(O2CEt)2 3 xH2O (0.40 g, 2.0 mmol) in H2O/EtCO2H (15/3 mL) was added solid Bi(NO3)3 3 5H2O (0.97 g, 2.0 mmol). The resulting white suspension was stirred for a total of 20 min, during which time solid NnBu4MnO4 (0.22 g, 0.6 mmol) was added in small portions, causing a rapid color change to dark brown. The final dark brown slurry was filtered and the filtrate left undisturbed to concentrate slowly by evaporation. After 10 days, X-ray-quality dark-brown plate-like crystals of 1 had appeared and were collected by filtration, washed with cold H2O (2 Â 2 mL) and Me2CO (2 Â 5 mL), and dried under a vacuum; the yield was 10%. Anal. Calcd for 1: C, 19.91; H, 2.84; N, 2.32%. Found: C, 20.15; H, 3.02; N, 2.24%. Selected IR data (cmÀ1): 3213 (mb), 2965 (m), 1535 (s), 1390 (vs), 1361 (m), 1300 (m), 1272 (m), 1235 (m), 1198 (m), 1047 (m), 966 (m), 934 (m), 906 (m), 806 (m), 772 (w), 733 (s), 639 (m), 606 (s), 579 (m), 519 (w), 475 (m), 449 (w), 416 (w). [Bi2Mn6O9(O2CPh)9(HO2CPh)(NO3)3] (2). Solid PhCO2H (2.00 g, 16.4 mmol) was dissolved in hot MeCN (50 mL) with stirring, and the resulting colorless solution was treated with solid Mn(O2CPh)2 3 2H2O (0.67 g, 2.0 mmol) and Bi(NO3)3 3 5H2O (0.97 g, 2.0 mmol), which caused a color change to orange. The solution was stirred at 70 °C for a total of 10 min, during which time solid NnBu4MnO4 (0.22 g, 0.6 mmol) was added in small portions. The resulting dark brown slurry was allowed to cool down at room temperature, filtered, and the filtrate layered with CH2Cl2 (50 mL). After five days, X-ray-quality dark-brown plate-like crystals of 2 3 4MeCN 3 2 CH2Cl2 had appeared and were collected by filtration, washed with MeCN (2 Â 5 mL) and CH2Cl2 (2 Â 5 mL), and dried under a vacuum; the yield was 30%. Anal. Calcd for 2 (solvent-free): C, 35.06; H, 2.32; N, 2.07%. Found: C, 35.15; H, 2.04; N, 2.34%. The crystal structure shows a 60:40% disorder of a carboxylate with a nitrate (vide infra), and this has been taken into account in the calculation of the expected elemental percentages. Selected IR data (cmÀ1): 3380 (mb), 1642 (m), 1596 (m), 1532 (s), 1491 (m), 1394 (vs), 1178 (m), 1069 (w), 1025 (m), 1000 (w), 937 (w), 858 (w), 825 (w), 717 (s), 688 (s), 634 (s), 611 (s), 523 (m), 444 (w), 416 (w). ARTICLE [BiMn10O8(O2CPh)17(HO2CPh)(H2O)] (3). Solid PhCO2H (2.00 g, 16.4 mmol) was dissolved in hot MeNO2 (50 mL) with stirring, and the resulting colorless solution was treated with solid Mn(O2CPh)2 3 2H2O (0.67 g, 2.0 mmol) and Bi(O2CMe)3 (0.77 g, 2.0 mmol), which caused a color change to orange. The solution was stirred at 80 °C for a total of 10 min, during which time solid NnBu4MnO4 (0.22 g, 0.6 mmol) was added in small portions. The resulting dark brown slurry was filtered and the filtrate left undisturbed to concentrate slowly by evaporation. After four days, X-rayquality brown needle-like crystals of 3 3 6PhCO2H had appeared and were collected by filtration, washed with MeNO2 (2 Â 3 mL) and CH2Cl2 (2 Â 5 mL), and dried under a vacuum; the yield was 60%. Anal. Calcd for 3 3 6PhCO2H: C, 52.85; H, 3.41%. Found: C, 53.04; H, 3.65%. Selected IR data (cmÀ1): 3380 (wb), 3063 (m), 2655 (w), 2544 (w), 1966 (w), 1915 (w), 1820 (w), 1690 (s), 1599 (vs), 1533 (sb), 1426 (sb), 1176 (s), 1069 (m), 1025 (m), 1001 (w), 938 (w), 841 (w), 816 (w), 721 (s), 683 (s), 634 (sb), 508 (m), 438 (w), 415 (w). X-Ray Crystallography. Data were collected on a Siemens SMART PLATFORM equipped with a CCD area detector and a graphite monochromator utilizing Mo KR radiation (λ = 0.71073 Å). Suitable crystals of 1, 2 3 4MeCN 3 2CH2Cl2, and 3 3 6PhCO2H were attached to glass fibers using silicone grease and transferred to a goniostat where they were cooled to 173 K for data collection. An initial search for reciprocal space revealed a monoclinic cell for 1 and 3 3 6PhCO2H and a tetragonal cell for 2 3 4MeCN 3 2CH2Cl2; space groups P21/n (1), P421/c (2 3 4MeCN 3 2CH2Cl2), and P21/c (3 3 6PhCO2H) were confirmed by the subsequent solution and refinement of the structures. Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the ω-scan method (0.3° frame width). The first 50 frames were remeasured at the end of data collection to monitor instrument and crystal stability (maximum correction on I was <1%). Absorption corrections by integration were applied on the basis of measured indexed crystal faces. The structures were solved by direct methods in SHELXTL623 and refined on F2 using full-matrix least squares. The non-H atoms were treated anisotropically, whereas the H atoms were placed in calculated, ideal positions and refined as riding on their respective C atoms. For 1, the asymmetric unit consists of the complete Bi2Mn6 cluster and no solvent molecules of crystallization. The hydrogen atom H38 involved in the O38 3 3 3 H38 3 3 3 O8 hydrogen bond was observed in a difference Fourier map and refined as riding on its parent atom. A total of 712 parameters were included in the structure refinement using 9489 reflections with I > 2σ(I) to yield an R1 and wR2 of 3.32 and 7.22%, respectively. For 2 3 4MeCN 3 2CH2Cl2, the asymmetric unit consists of the complete Bi2Mn6 cluster, and four MeCN and two CH2Cl2 molecules of crystallization. The solvent molecules are disordered and could not be modeled properly, thus the program SQUEEZE,24 a part of the PLATON package of crystallographic software, was used to calculate the solvent disorder area and remove its contribution to the overall intensity data. One Ph ring was disordered at two positions with 50:50% refined occupancies. Another disorder involved a benzoate and a nitrate group at the same site with 60:40% occupancies, respectively. A total of 626 parameters were refined using 9216 reflections with I > 2σ(I) to yield an R1 and wR2 of 7.40 and 15.40%, respectively. For 3 3 6PhCO2H, the asymmetric unit consists of the complete BiMn10 cluster and six PhCO2H lattice molecules. The latter could not be modeled properly; thus the program SQUEEZE was again used to calculate the solvent disorder area and remove its contribution to the overall intensity data. The total number of electrons per asymmetric unit was calculated to be 435. This number and the difference Fourier map leads to an estimate of six PhCO2H lattice molecules. Additionally, one phenyl group was disordered and refined in two parts with 61:39% occupancies. A total of 1598 parameters were included in the final cycle of refinement using 8379 reflections with I > 2σ(I) to yield an R1 and wR2 of 6.57 and 16.30%, respectively. 5273 dx.doi.org/10.1021/ic200656q |Inorg. Chem. 2011, 50, 5272–5282 Inorganic Chemistry ARTICLE Table 1. Crystallographic Data for 1, 2 3 4MeCN 3 2CH2Cl2, and 3 3 6PhCO2H parameter 1 2 3 formulaa C30H51N3O38Mn6Bi2 C77.2H69N7.4O40.4Cl4Mn6Bi2 C168H128O57Mn10Bi fw, g molÀ1a 1809.34 2593.25 3817.08 cryst syst monoclinic tetragonal monoclinic space group P21/n P421/c P21/c a, Å 12.5042(14) 26.2209(15) 16.8942(14) b, Å 23.884(3) 26.2209(15) 25.356(2) c, Å 17.900(2) 26.591(3) 35.234(3) β, deg V, Å3 94.770(2) 5327.4(10) 90 18282(3) 92.064(2) 15083(2) Z 4 8 4 T, K 173(2) 173(2) 173(2) radiation, Åb 0.71073 0.71073 0.71073 Fcalc, g cmÀ3 2.256 1.884 1.681 μ, mmÀ1 8.063 4.846 2.065 R1c,d 0.0332 0.0740 0.0657 wR2e 0.0722 0.1540 0.1630 Including solvate molecules. b Graphite monochromator. c I > 2σ(I). d R1 = ∑(||Fo| À |Fc||)/∑|Fo|. e wR2 = [∑[w(Fo2 À Fc2)2]/∑[w(Fo2)2]]1/2, w = 1/[σ 2(Fo2) þ [(ap)2 þbp], where p = [max(Fo2, 0) þ 2Fc2]/3. a Unit cell data and structure refinement details for the complexes are collected in Table 1. Physical Measurements. Infrared spectra were recorded in the solid state (KBr pellets) on a Nicolet Nexus 670 FTIR spectrometer in the 400À4000 cmÀ1 range. Elemental analyses (C, H, and N) were performed on a Perkin-Elmer 2400 Series II Analyzer. Variable-temperature dc and ac magnetic susceptibility data were collected at the University of Florida using a Quantum Design MPMS-XL SQUID susceptometer equipped with a 7 T magnet and operating in the 1.8À300 K range. Samples were embedded in solid eicosane to prevent torquing. The ac magnetic susceptibility measurements were performed in an oscillating ac field of 3.5 Oe and a zero dc field. The oscillation frequencies were in the 5À1488 Hz range. Pascal’s constants were used to estimate the diamagnetic corrections, which were subtracted from the experimental susceptibilities to give the molar paramagnetic susceptibilities (χM). ’ RESULTS AND DISCUSSION complex [Bi2Mn6O9 (O2CPh)9(HO2CPh)(NO3)3] (2) in a superior (∼30%) yield. Both 1 and 2 are at the BiIII2MnIV6 oxidation level (vide infra), although the MnII/MnVII ratio employed gives an average Mn oxidation state in the solution of only Mn3.15þ, appreciably lower than the Mn4þ. We normally do not expect atmospheric O2 to generate Mn4þ in such reactions, and our feeling is that the MnIV is likely forming from disproportionation of MnIII; this is consistent with the low yields (10À30% based on total Mn) of isolated products (eq 1). In addition, the filtrates were still intensely colored, but we did not pursue isolation from them of additional crops of 1 or 2, or other products. Instead, we changed the MnII/MnVII ratio to 3:2, which gives an average Mn oxidation state of þ4, but these reactions led to even smaller isolated yields of 1 and 2 (∼5À10%), with the main product now being the [Mn12O12(O2CR)16(H2O)4] complexes; the latter cocrystallized in yields as large as 50À60% (based on total available Mn). 10Mn2þ þ 3Mn7þ þ 2Bi3þ f Bi2 MnIV 6 Syntheses. Many reactions under various conditions and reagent ratios were explored before the procedures described below were developed. These were all variations, to some degree or other, of the comproportionation reaction between MnII and MnVII that is the synthetic procedure for [Mn12O12(O2CMe)16(H2O)4] (MnIII8MnIV4).25 The latter involves the reaction in aqueous acetic acid between Mn(O2CMe)2 and KMnO4 in a MnII/MnVII ratio that gives an average of Mn3.33þ. We have screened various modifications, such as in the MnII/MnVII ratio, the carboxylate identity, and others, and added a BiIII source to target a mixed-metal product. The reaction between Mn(O2CEt)2 3 xH2O, NnBu4MnO4, and Bi(NO3)3 3 5H2O in a 10:3:10 molar ratio in 17% aqueous propionic acid led to subsequent isolation of black crystals of [Bi2Mn6O9(O2CEt)9(HO2CEt)(NO3)3] (1) in small (∼10%) but reproducible yields. An analogous reaction between Mn(O2CPh)2 3 2H2O, NnBu4MnO4, and Bi(NO3)3 3 5H2O in the same 10:3:10 ratio but in hot PhCO2H/MeCN (heated to ensure dissolution of all benzoic acid and thus prevent formation of insoluble Mn oxide precipitates) gave the isostructural þ 3Mn3þ þ 4Mn2þ ð1Þ NO3À ions and the latter are thus Since 1 and 2 contain bound essential for yielding these products, the Bi(NO3)3 3 5H2O reagent was replaced with Bi(O2CMe)3 to possibly divert the reactions to different types of clusters. Indeed, the comproportionation reaction between Mn(O2CPh)2 3 2H2O, NnBu4MnO4, and Bi(O2CMe)3 in a 10:3:10 ratio in hot PhCO2H/MeNO2 led to the subsequent isolation of [BiMn10O8(O2CPh)17(HO2CPh)(H2O)] (3) in good (∼60%) yield. Complex 3 contains BiIIIMnIII10, the MnIII oxidation level now being that expected from the average of þ3.15 from the employed MnII/MnVII ratio. This rationalizes the much larger isolated yield of 3 compared with 2 and suggests that the presence of the hard nitrate ion facilitates disproportionation and formation of a MnIV-containing product. An analogous reaction with Mn(O2CEt)2 3 xH2O and EtCO2H in place of Mn(O2CPh)2 3 2H2O and PhCO2H, respectively, also led to a dark brown solution, but we were unable to isolate any pure products, such as [BiMn10O8(O2CEt)17(HO2CEt)(H2O)], the propionate analogue of 3. 5274 dx.doi.org/10.1021/ic200656q |Inorg. Chem. 2011, 50, 5272–5282 Inorganic Chemistry ARTICLE Table 2. Selected Interatomic Distances (Å) for 1 parameter parameter Mn(1) 3 3 3 Mn(2) Mn(2) 3 3 3 Mn(3) Mn(3) 3 3 3 Mn(4) 3.303(1) Mn(4) 3 3 3 Mn(5) Mn(5) 3 3 3 Mn(6) Mn(6) 3 3 3 Mn(1) 2.733(1) Bi(1) 3 3 3 Mn(1) Bi(1) 3 3 3 Mn(2) Bi(1) 3 3 3 Mn(3) Bi(1) 3 3 3 Mn(4) 3.416(3) 3.497(1) Mn(1)ÀO(1) Mn(1)ÀO(3) Mn(1)ÀO(4) 2.697(2) 3.295(2) 3.295(3) 2.717(2) Bi(1) 3 3 3 Mn(5) Bi(1) 3 3 3 Mn(6) Bi(2) 3 3 3 Mn(1) 3.468(1) Bi(2) 3 3 3 Mn(2) Bi(2) 3 3 3 Mn(3) Bi(2) 3 3 3 Mn(4) 3.610(1) 3.427(2) 3.721(1) 3.562(2) 3.445(3) Bi(2) 3 3 3 Mn(5) Bi(2) 3 3 3 Mn(6) Bi(1) 3 3 3 Bi(2) 3.708(2) 3.677(2) 1.959(3) Mn(5)ÀO(24) 1.853(3) 1.837(3) Mn(5)ÀO(31) 1.932(3) 1.934(4) Mn(5)ÀO(33) 1.924(4) Mn(1)ÀO(36) 1.937(3) Mn(6)ÀO(24) 1.853(3) Mn(1)ÀO(37) 1.820(3) Mn(6)ÀO(32) 1.931(3) Mn(1)ÀO(38) Mn(2)ÀO(2) 1.869(3) 1.956(3) Mn(6)ÀO(34) Mn(6)ÀO(35) 1.949(4) 1.939(3) 3.492(3) 3.522(2) 3.478(2) Mn(2)ÀO(3) 1.853(3) Mn(6)ÀO(37) 1.807(3) Mn(2)ÀO(5) 1.962(3) Mn(6)ÀO(38) 1.869(3) Mn(2)ÀO(6) 1.832(3) Bi(1)ÀO(3) 2.409(3) Mn(2)ÀO(12) 1.941(3) Bi(1)ÀO(6) 2.628(3) Mn(2)ÀO(23) 1.833(3) Bi(1)ÀO(7) 2.468(3) Mn(3)ÀO(6) 1.838(3) Bi(1)ÀO(9) 2.416(4) Mn(3)ÀO(13) Mn(3)ÀO(14) 1.927(3) 1.956(3) Bi(1)ÀO(10) Bi(1)ÀO(16) 2.602(5) 2.588(3) 2.482(3) Mn(3)ÀO(17) 1.852(3) Bi(1)ÀO(17) Mn(3)ÀO(21) 1.939(3) Bi(1)ÀO(24) 2.380(3) Mn(3)ÀO(23) 1.826(3) Bi(1)ÀO(38) 2.474(3) 2.651(3) Mn(4)ÀO(15) Description of Structures. A partially labeled representation and a stereoview of complex 1 are shown in Figure 1. Selected interatomic distances are listed in Table 2. Complex 1 crystallizes in monoclinic space group P21/n with the [Bi2Mn6O9(O2CEt)9(HO2CEt)(NO3)3] molecule lying on a crystallographic inversion center. The core consists of a near-planar MnIV6 wheel (displacement of Mn atoms from the Mn6 least-squares plane is 0.009À0.044 Å), with the edges bridged alternately by {(μ3O)2(μ-O2CEt)} and {(μ4-O)(μ-O2CEt)2} ligand sets giving Mn 3 3 3 Mn separations of 2.697À2.733 and 3.295À3.303 Å, respectively. The nine oxide ions are also all bound to one or both of the two BiIII ions, Bi1 and Bi2, which lie 1.725 and 1.946 Å, respectively, out of the Mn6 plane (Figure 2, top). The complex thus contains a [Bi2Mn6(μ4-O)3(μ3-O)6]12þ core (Figure 2, bottom) of virtual D3h symmetry. Ligation at Bi1 is completed by a monodentate EtCO2H and a bidentate-chelating NO3À and at Bi2 by two bidentate-chelating NO3À groups. The MnÀO2À (1.807À1.878 Å) and propionate MnÀO (1.924À1.962 Å) bond lengths are typical of MnIV values,26 while the BiIIIÀO bonds are in the range 2.326À2.862 Å, in agreement with values in the literature.27 All Mn atoms are six-coordinate with distorted octahedral geometry, whereas Bi1 and Bi2 are nine- and 10-coordinate, respectively. Bi(2)ÀO(3) 1.841(3) Bi(2)ÀO(17) 2.470(3) Mn(4)ÀO(17) 1.840(3) Bi(2)ÀO(22) 2.412(3) Mn(4)ÀO(18) Mn(4)ÀO(20) Figure 1. Partially labeled PovRay representation (top) and stereopair (bottom) of complex 1, with H atoms omitted for clarity. Color scheme: BiIII, yellow; MnIV, dark green; O, red; N, light green; C, gray. 1.943(3) Mn(4)ÀO(16) 1.952(3) 1.924(3) Bi(2)ÀO(23) Bi(2)ÀO(24) 2.656(3) 2.579(3) 2.326(3) Mn(4)ÀO(22) 1.878(3) Bi(2)ÀO(25) Mn(5)ÀO(16) 1.828(3) Bi(2)ÀO(26) 2.692(4) Mn(5)ÀO(19) 1.928(4) Bi(2)ÀO(28) 2.698(4) Mn(5)ÀO(22) 1.872(3) Bi(2)ÀO(29) 2.365(4) Bi(2)ÀO(37) 2.862(4) The metal oxidation states and the protonation levels of O2À ions were suggested by the metric parameters and charge balance considerations and confirmed by bond valence sum (BVS) calculations (Table 3).28 BVS values for O2À atoms are typically 1.8À2.0, although participation as acceptor atoms in H bonds can decrease this value slightly. In 1, we note that the μ4-O2À ions give a slightly greater value of ∼2.2 (which does not affect their assignment as O2À), whereas the μ3-O2À ions are in the normal range. The monodentate EtCO2H ligand on Bi1 binds through its CdO group (C7ÀO7 = 1.251(7) Å), and its COH group (C7ÀO8 = 1.338 (7) Å) forms a H bond to oxide O38 (O7 3 3 3 O38 = 2.707(5) Å). The H atom (H38) was observed in a difference Fourier map and appeared to lie slightly closer to the oxide O8 (1.279 vs 1.528 Å), but we nevertheless disfavor a suggestion that formally the oxide O38 is really OHÀ and the EtCO2H is EtCO2À. The O38 BVS (1.79), the binding to Bi through the CdO, and the low basicity (vs EtCO2À) 5275 dx.doi.org/10.1021/ic200656q |Inorg. Chem. 2011, 50, 5272–5282 Inorganic Chemistry ARTICLE Figure 2. (Top) The Bi2Mn6 topology, showing the MnIV6 leastsquares plane (purple) of the wheel description. The black dashed lines are the Bi 3 3 3 Mn vectors. (Bottom) Labeled PovRay representation of the complete [Bi2Mn6(μ4-O)3(μ3-O)6]12þ core of 1. Color scheme: BiIII, yellow; MnIV, dark green; O, red. Table 3. Bond Valence Sum (BVS)a,b Calculations for Mn and Selected O Atoms of 1 atom MnII MnIII MnIV Mn1 4.29 3.92 4.12 Mn2 Mn3 4.26 4.33 3.90 3.96 4.09 4.15 Mn4 4.24 3.88 4.07 Mn5 4.31 3.94 4.14 Mn6 4.31 3.94 4.14 atom assignment O3 2.17 O2À (μ4) O6 1.80 O2À (μ3) O16 O17 1.83 2.23 O2À (μ3) O2À (μ4) O22 1.82 O2À (μ3) O23 1.81 O2À (μ3) O24 2.22 O2À (μ4) O37 1.79 O2À (μ3) O38 a BVS 1.78 O2À (μ3)c The underlined value is the one closest to the charge for which it was calculated. The oxidation state can be taken as the nearest whole number to the underlined value. b An O BVS in the ∼1.8À2.0, ∼1.0À1.2, and ∼0.2À0.4 ranges is indicative of non-, single- and double-protonation, respectively, but can be altered somewhat by hydrogen bonding. c See the text. Figure 3. Partially labeled PovRay representation (top) and stereopair (bottom) of complex 2, with H atoms omitted for clarity. Color scheme: BiIII, yellow; MnIV, dark green; O, red; N, green; C, gray. expected for an O2À bridging three high oxidation state metal atoms all suggest O38 is not formally protonated and that the EtCO2H is protonated. In addition to the above “di-Bi-capped Mn6 wheel” description of the [Bi2Mn6O9]12þ core, an alternative description can be presented: the [Bi2Mn6O9] unit (Figure 2, bottom) can be considered as three [Bi2Mn2(μ3-O)4] distorted cubanes fused together at one of their faces; i.e., each cubane fuses half of one face with one neighbor and the other half of that face with the other neighbor. Finally, there are no significant intermolecular interactions, only weak ones involving CÀH bonds. A partially labeled representation and a stereoview of complex 2 are shown in Figure 3. The molecule is essentially isostructural with complex 1 and thus will not be discussed here. The main differences between 2 and 1 are the benzoate vs propionate identity of the carboxylate employed, which causes a greater separation between neighboring molecules in the crystal, the binding of the PhCO2H to one Bi as a bidentate chelate rather than monodentate ligand, and the extensive disorder observed in some ligands and the many solvent molecules of crystallization. Again, BVS calculations, charge considerations, and inspection of metric parameters confirm that the Mn and Bi atoms of complex 2 are all in þ4 and þ3 oxidation states, respectively. The heterometallic [M6M02O9] cores of 1 and 2 have never been seen before in the cluster chemistry of any metals. In addition, complexes 1 and 2 are only the second and third examples of a MnIV6 wheel. The one previous Mn6 wheel at this oxidation level 5276 dx.doi.org/10.1021/ic200656q |Inorg. Chem. 2011, 50, 5272–5282 Inorganic Chemistry ARTICLE Table 4. Selected Interatomic Distances (Å) for 3 3 6PhCO2H parameter parameter Mn 3 3 3 Mn 3.047(3) À6.915(3) Bi 3 3 3 Mn 3.240(2) À3.758(2) Mn(1)ÀO(1) 1.833(7) Mn(6)ÀO(38) 1.957(8) Mn(1)ÀO(9) 1.955(7) Mn(7)ÀO(6) 1.824(7) Mn(1)ÀO(10) 1.952(8) Mn(7)ÀO(8) 1.912(7) Mn(1)ÀO(13) 2.134(9) Mn(7)ÀO(14) 2.127(8) Mn(1)ÀO(15) 2.363(9) Mn(7)ÀO(36) 1.940(8) Mn(1)ÀO(46) 1.979(8) Mn(7)ÀO(41) 2.239(7) Mn(2)ÀO(1) 1.836(7) Mn(2)ÀO(2) 2.301(8) Mn(7)ÀO(43) 1.983(8) Mn(8)ÀO(7) 1.945(8) Mn(2)ÀO(3) 1.891(7) Mn(8)ÀO(8) Mn(2)ÀO(11) 1.991(8) Mn(8)ÀO(34) 2.275(7) 1.919(7) Mn(2)ÀO(16) 2.122(1) Mn(8)ÀO(39) 1.968(8) Mn(2)ÀO(18) 1.956(8) Mn(8)ÀO(40) 1.924(8) Mn(3)ÀO(3) 1.832(7) Mn(8)ÀO(44) 2.186(7) Mn(3)ÀO(4) 1.910(7) Mn(9)ÀO(7) Mn(3)ÀO(19) 1.941(8) Mn(3)ÀO(20) 2.132(8) Mn(9)ÀO(9) 1.908(8) Mn(9)ÀO(12) 1.930(8) 1.930(7) Mn(3)ÀO(25) 2.343(8) Mn(9)ÀO(17) 2.352(9) Mn(3)ÀO(27) 1.944(8) Mn(9)ÀO(23) 1.965(9) Mn(4)ÀO(4) 1.913(7) Mn(9)ÀO(45) 2.198(9) Mn(4)ÀO(5) 1.853(8) Mn(10)ÀO(8) 1.897(7) Mn(4)ÀO(25) 2.380(8) Mn(10)ÀO(9) 1.916(7) Mn(4)ÀO(29) 1.942(8) Mn(10)ÀO(15) 2.167(8) Mn(4)ÀO(31) 1.947(8) Mn(4)ÀO(35) 2.226(8) Mn(10)ÀO(42) 1.952(8) Mn(10)ÀO(44) 2.191(8) Mn(5)ÀO(4) 1.886(7) Mn(10)ÀO(47) 1.974(8) Mn(5)ÀO(6) 1.830(7) was [CeMn6O9(O2CMe)9(NO3)(H2O)2], which has a single CeIV atom at the center and lying 1.513 Å above the Mn6 plane.29 In contrast, 1 and 2 are the first examples of a cyclic M6M02 unit, i.e., a transition metal M6 wheel with two central M0 atoms on either side of the wheel plane. They are related to the CeMn6 compound in that they have a second heteroatom on the other side of the Mn6 plane, which suggests that under the right conditions the analogous compound [Ce2Mn6O9(O2CMe)9(NO3)5(H2O)] with CeIV and/or CeIII might also be attainable. A Cu6 wheel with a single central lanthanide atom is also known.30 A partially labeled representation and a stereoview of complex 3 are shown in Figure 4. Selected interatomic distances are listed in Table 4. Complex 3 crystallizes in the monoclinic space group P21/ c with the BiMn10 molecule in a general position. It contains one BiIII and 10 MnIII atoms held together by four μ4-O2À (O4, O7, O8, O9) and four μ3-O2À (O1, O3, O5, O6) ions to give a low symmetry [BiMn10O8]17þ core. There are a variety of familiar smaller nuclearity units that can be seen as fragments of the core, including a [BiMn3(μ3-O)2]8þ butterfly unit (Bi1, Mn1, Mn2, Mn3, O1, O3), four [BiMn3(μ4-O)]10þ tetrahedra (Bi1, Mn1, Mn9, Mn10, O9/Bi1, Mn3, Mn4, Mn5, O4/Bi1, Mn6, Mn8, Mn9, O7/Bi1, Mn7, Mn8, Mn10, O8), and two [BiMn2(μ3-O)]7þ triangular units (Bi1, Mn4, Mn6, O5/Bi1, Mn5, Mn7, O6), all fused together and linked to adjacent units by sharing common Mn and Bi vertices. As a result, the single nine-coordinate BiIII atom is Bi(1)ÀO(1) 2.377(6) Mn(5)ÀO(21) 2.117(8) Figure 4. Partially labeled PovRay representation (top) and stereopair (bottom) of complex 3, with H atoms omitted for clarity. Color scheme: BiIII, yellow; MnIII, blue; O, red; C, gray. Bi(1)ÀO(3) 2.190(7) Mn(5)ÀO(28) 1.986(8) Bi(1)ÀO(4) 2.678(7) Mn(5)ÀO(35) 2.492(7) Bi(1)ÀO(5) 2.350(7) Mn(5)ÀO(37) 1.966(8) Bi(1)ÀO(6) 2.415(8) Mn(6)ÀO(5) 1.848(8) Mn(6)ÀO(7) 1.920(7) Bi(1)ÀO(7) Bi(1)ÀO(8) 2.716(7) 2.826(8) Mn(6)ÀO(22) 2.097(1) Bi(1)ÀO(9) 2.894(7) Mn(6)ÀO(30) 1.928(8) Bi(1)ÀO(17) 2.491(9) Mn(6)ÀO(34) 2.225(8) encapsulated inside a MnIII10 cage, held in place by the eight O2À ions and a carboxylate O atom (O17) that bridge it to the Mn atoms (Figure 5). Peripheral ligation about the [BiMn10O8]17þ core is provided by a total of 17 bridging PhCO2À groups, one terminal PhCO2H group, and one H2O molecule. The PhCO2H group binds to Mn3 with its O27 and forms a particularly short H bond to the unbound O atom of a neighboring benzoate (O26 3 3 3 O24 = 2.413(10) Å). The terminal H2O (O2) on Mn2 forms a H bond to the Mn-bound O20 of a neighboring carboxylate (O2 3 3 3 O20 = 2.650(10) Å). The PhCO2À groups adopt an impressive variety of bridging modes, and these are shown in Figure 6. Twelve PhCO2À groups bridge in the common η1:η1:μ mode (I), three in the rarer η1:η2:μ3 mode (II) across Mn3 or BiMn2 units, one in the extremely rare η2:η2:μ4 mode (III), and the final one in an η2:μ mode (IV) leaving O24 unbound. Thus, including the monatomic ORÀ bridge (R = PhCOÀ), 3 contains an overall [BiMn10(μ4-O)4(μ3-O)4(μ-OR)6]11þ core (Figure 5). The structure does not form any significant intermolecular H 5277 dx.doi.org/10.1021/ic200656q |Inorg. Chem. 2011, 50, 5272–5282 Inorganic Chemistry ARTICLE Figure 5. Labeled PovRay representation of the complete [BiMn10(μ4-O)4(μ3-O)4(μ-OR)6]11þ unit. Color scheme: BiIII, yellow; MnIII, blue; O, red; C, gray. Figure 7. A space-filling representation of 3. Color scheme: BiIII, yellow; MnIII, blue; O, red; C, gray; H, purple. Table 5. Bond Valence Sum (BVS)a,b Calculations for Mn and Selected Oxygen Atoms in 3 atom MnII MnIII MnIV Mn1 3.16 2.89 3.04 Mn2 3.29 3.01 3.16 Mn3 3.33 3.04 3.20 Mn4 Mn5 3.17 3.22 2.90 2.94 3.04 3.09 Mn6 3.39 3.10 3.26 Mn7 3.36 3.07 3.22 Mn8 3.08 2.81 2.95 Mn9 3.06 2.80 2.94 Mn10 3.19 2.92 3.06 BVS O1 O3 bonds, only weak contacts between CÀH bonds and the π system of PhCO2À groups. Finally, a space-filling representation (Figure 7) shows that 3 has an aesthetically pleasing, near-spherical structure of ∼20 Å diameter. The Mn atoms are all six-coordinate with near-octahedral geometry. The metal oxidation states and the protonation levels of O2À and H2O groups were determined by BVS calculations (Table 5),28 inspection of metric parameters, charge balance considerations, and clear observation of JahnÀTeller (JT) distortion axes at all of the Mn ions. The JT distortions all take the form of axial elongations, as is almost always the case for highspin MnIII, with JT elongated bonds being 0.1À0.4 Å longer than the other MnIIIÀO bonds (∼1.8À2.0 Å). Further, the axial positions of the MnO6 distorted octahedra are all occupied by the 1.92 2.12 O2À (μ3) O2À (μ3) O4 1.99 O2À (μ4) O5 1.89 O2À (μ3) O6 1.91 O2À (μ3) O7 1.83 O2À (μ4) O8 1.89 O2À (μ4) O9 Figure 6. The bridging modes displayed by the PhCO2À groups in complex 3. assignment 1.79 O2À (μ4) 0.21 H2O (η1) O2 a b See footnote a of Table 3. See footnote b of Table 3. O atoms of the carboxylate and water groups. Thus, as is almost always the case, the JT elongation axes avoid the MnIIIÀO2À bonds, the shortest and strongest in the molecule.31 The 10 JT elongation axes do not align parallelly but instead in a somewhat random manner (Figure S1, Supporting Information), suggesting the axial zero-field parameter (D) for 3 is very likely to be very 5278 dx.doi.org/10.1021/ic200656q |Inorg. Chem. 2011, 50, 5272–5282 Inorganic Chemistry ARTICLE Figure 8. χMT vs T plot for complex 2 in a 1 kG dc field. Figure 9. χMT vs T plot for complex 3 3 6PhCO2H in a 1 kG dc field. small (<0.1 cmÀ1). Complex 3 joins a handful of structurally characterized, heterometallic undecanuclear metal complexes,32 and it is the first with such a metal core topology and a 10:1 metal composition. Further, the MnIII10 shell within the structure of 3 becomes a new member of the small family of decanuclear Mn clusters at the 3þ oxidation state level.25b,33 Magnetic Susceptibility Studies on Complexes 1À3. Variable-temperature, solid-state magnetic susceptibility measurements were performed on powdered polycrystalline samples of dried 1, 2, and 3 3 6PhCO2H restrained in eicosane to prevent torquing, in a 1 kOe (0.1 T) field and in the 5.0À300 K range. All paramagnetism is associated with the Mn ions because BiIII is diamagnetic. The magnetic data for 1 and 2 are essentially identical, and therefore only those of the latter will be discussed in detail. The data for 1 are available in the Supporting Information. The obtained data for 2 are shown as χMT versus T in Figure 8. χMT steadily decreases from 8.91 cm3 K molÀ1 at 300 K to 0.76 cm3 K molÀ1 at 5.0 K, which indicates the presence of dominant antiferromagnetic exchange interactions within the molecule. The calculated spin-only (g = 2.0) χMT for a MnIV6 cluster of noninteracting metal ions is 11.25 cm3 K molÀ1, appreciably higher than the experimental value at 300 K and thus suggestive of strong antiferromagnetic interactions, as indeed expected for oxide-bridged MnIV2 interactions. The χMT value at 5.0 K strongly indicates an S = 0 ground state spin value for 2, which is as found previously for [CeMn6O9(O2CMe)9(NO3) (H2O)2]. The exchange interactions in the MnIV6 wheel of the latter compound have already been studied in extensive detail, having been determined experimentally by fitting the magnetic susceptibility data by matrix diagonalization, and theoretically by ZILSH calculations.29 The obtained values were found to be weakly antiferromagnetic, J1 = À5.8(3) cmÀ1 and J2 = À0.63(10) cmÀ1 (H = À2J^i 3 ^j convention), where J1 and J2 are the interactions SS for the {Mn2O2(O2CR)} and {Mn2O(O2CR)2} bridged pairs. Given the analogous S = 0 ground states of 1 and 2, and the fact that we did not anticipate that their interactions would be particularly different from the CeMn6 compound, we did not consider it worthwhile to also carry out a fitting of their data by matrix diagonalization. The topology of the Mn6 wheel also does not allow application of the more convenient Kambe method.34 For 3 3 6PhCO2H, the obtained data are shown as χMT versus T in Figure 9. χMT steadily decreases from 26.35 cm3 K molÀ1 at 300 K to 4.66 cm3 K molÀ1 at 5.0 K. Again, the 300 K value is much less than the spin-only (g = 2) value of 30 cm3 K molÀ1 for 10 noninteracting MnIII ions, indicating the presence of dominant antiferromagnetic exchange interactions and a low, but likely nonzero, ground state S. The high nuclearity and low symmetry of the complex preclude determination of the individual pairwise Mn2 exchange interaction parameters, and we concentrated instead on characterizing the ground state spin S by fits of low temperature magnetization data. Magnetization (M) data were collected in the 1À70 kG magnetic field and 1.8À10.0 K temperature ranges. However, we could not get an acceptable fit using data collected over the whole field range, which is a common problem caused by low-lying excited states in high nuclearity complexes, especially if some have an S value greater than that of the ground state, as is the case for 3 3 6PhCO2H on the basis of Figure 9. A common solution is to only use data collected with low fields (e1.0 T), as previously reported for high-nuclearity MnIII clusters,35 but in this case, it was still not possible to obtain a satisfactory fit assuming that only the ground state is populated. This suggests particularly low-lying excited states in this compound. Thus, we turned to ac susceptibility measurements as an alternative means of determining the ground state. As we have described before on multiple occasions,35 ac susceptibility studies are a powerful complement to dc methods for determining ground states because they preclude any complications arising from low-lying excited states and/or the presence of a dc field. These were performed in the 1.8À15 K range using a 3.5 G ac field oscillating at frequencies in the 50À1000 Hz range. If the magnetization vector stays in phase with the oscillating field, there is no out-of-phase susceptibility (χ00 ) signal, and the in-phase M susceptibility (χ0M) is equal to the dc susceptibility. Figure 10 shows the in-phase ac susceptibility for 3 3 6PhCO2H, plotted as χ0MT versus T, together with the plot for 2 for comparison. For 2, χ0MT decreases only slightly in this temperature range, from ∼0.5 to ∼0.1 cm3 K molÀ1, and is clearly heading for ∼0 cm3 K molÀ1, confirming an S = 0 ground state that is well isolated from excited states; i.e., there is little population of the latter up to 15 K. In contrast, χ0MT for 3 3 6PhCO2H decreases steeply from ∼7.5 cm3 K molÀ1 at 15 K to under 3 cm3 K molÀ1 at 1.8 K, indicating extensive of depopulation of low-lying excited states with S greater than the ground state and confirming the latter as the reason for the poor magnetization fits. Extrapolation of the χ0MT 5279 dx.doi.org/10.1021/ic200656q |Inorg. Chem. 2011, 50, 5272–5282 Inorganic Chemistry ARTICLE access to structurally interesting heterometallic Bi/Mn clusters and suggests that further studies are warranted as a potential route to new structural types. Indeed, the work described represents merely our first steps in a full development of oxidebridged Bi/Mn molecular cluster chemistry, and results to date augur well for possible access to molecular analogs of the multifunctional Bi/Mn/O solids that are of such great interest in materials science. ’ ASSOCIATED CONTENT Supporting Information. Structural and magnetism figures and X-ray crystallographic files in CIF format for complexes 1, 2 3 4MeCN 3 2CH2Cl2, and 3 3 6PhCO2H. This material is available free of charge via the Internet at http://pubs.acs.org. S b ’ AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]fl.edu. ’ ACKNOWLEDGMENT This work was supported by NSF Grant CHE-0910472. ’ REFERENCES Figure 10. In-phase ac susceptibility (χ0M) as χ0MT vs T for 2 (top) and 3 3 6PhCO2H (bottom) at the indicated frequencies. plot from above 2 to 0 K gives a value of ∼2.6 cm3 K molÀ1, which is consistent with an S = 2 ground state and g < 2, as expected for a MnIII cluster; the spin-only (g = 2.0) χ0MT for S = 1, 2, and 3 states is 1.0, 3.0, and 6.0 cm3 K molÀ1, respectively. Thus, complex 3 3 6PhCO2H has a small ground state spin and, in combination with only the small anisotropy suggested by the orientation of the 10 MnIII JT axes, should not result in any significant barrier to magnetization relaxation. This is confirmed by the absence of outof-phase ac susceptibility signals down to 1.8 K (Figure S4). ’ CONCLUSIONS The described work has led to the discovery of the first polynuclear Bi/Mn complexes at high (MnIII/IV) oxidation states. On the basis of the two structural types obtained to date, at least, the incorporation of BiIII into Mn carboxylate cluster chemistry leads to products that are not structurally congruent with any currently known Mn or Mn/Ln (Ln = lanthanide) carboxylate cluster. The Bi2Mn6 and BiMn10 topologies are structurally very interesting, although they do not correspond to fragments of the structure of a mixed Bi/Mn oxide. Further, in spite of these first Bi/Mn molecular clusters not having particularly exciting magnetic properties, i.e., they are not new SMMs, they do not have particularly high ground state spin values, etc.; the described work does indicate that the use of BiIII provides (1) (a) Ferreira, K. N.; Iverson, T. 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