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High-Nuclearity Ce/Mn and Th/Mn Cluster Chemistry: Preparation of Complexes with [Ce4Mn10O10(OMe)6]18+ and [Th6Mn10O22(OH)2]18+ Cores Abhudaya Mishra,† Anastasios J. Tasiopoulos,† Wolfgang Wernsdorfer,‡ Khalil A. Abboud,† and George Christou*,† Department of Chemistry, UniVersity of Florida, GainesVille, Florida 32611-7200, and Laboratoire Louis Ne´ el-CNRS, BP 166, 25 AVenue des Martyrs, 38042 Grenoble, Cedex 9, France Received October 11, 2006
The syntheses, structures, and magnetic properties are reported of the mixed-metal complexes [Ce4Mn10O10(OMe)6(O2CPh)16(NO3)2(MeOH)2(H2O)2] (1) and [Th6Mn10O22(OH)2(O2CPh)16-(NO3)2(H2O)8] (2), which were both prepared by the reaction of (NBun4)[Mn4O2(O2CPh)9(H2O)] (3) with a source of the heterometal in MeCN/MeOH. Complexes 1 and 2 crystallize in the monoclinic space group C2/c and the triclinic space group P1h, respectively. Complex 1 consists of 10 MnIII, 2 CeIII, and 2 CeIV atoms and possesses a very unusual tubular [Ce4Mn10O10(OMe)6]18+ core. Complex 2 consists of 10 MnIV and 6 ThIV atoms and possesses a [Th6Mn10O22(OH)2]18+ core with the metal atoms arranged in layers with a 2:3:6:3:2 pattern. Peripheral ligation around the cores is provided by 16 bridging benzoates, 2 chelating nitrates, and either (i) 2 each of terminal H2O and MeOH groups in 1 or (ii) 8 terminal H2O groups in 2. Complex 1 is the largest mixed-metal Ce/Mn cluster and the first 3d/4f cluster with mixed-valency in its lanthanide component, while complex 2 is the first Th/Mn cluster and the largest mixed transition metal/actinide cluster to date. Solid-state dc and ac magnetic susceptibility measurements on 1 and 2 establish that they possess S ) 4 and 3 ground states, respectively. Ac susceptibility studies on 1 revealed nonzero frequency-dependent out-ofphase (χM′′) signals at temperatures below 3 K; complex 2 displays no χM′′ signals. However, single-crystal magnetization vs dc field scans at variable temperatures and variable sweep-rates down to 0.04 K on 1 revealed no noticeable hysteresis loops, except very minor ones at 0.04 K assignable to weak intermolecular interactions propagated by hydrogen bonds involving CeIII-bound ligands. Complex 1 is thus concluded not to be a singlemolecule magnet (SMM), and the combined results thus represent a caveat against taking such ac signals as sufficient proof of a SMM.
Introduction High-nuclearity transition metal cluster chemistry has been attracting intense interest during the last several years. This is due to the combination of the aesthetically pleasing structures that many such molecular clusters possess and the often unusual and even novel magnetic properties that some of them display. In particular, some of these clusters have been found to be single-molecule magnets (SMMs), which are individual molecules capable of functioning as nanoscale magnetic particles and which thus represent a molecular approach to nanomagnetism.1 Such molecules behave as magnets below their blocking temperature (TB), exhibiting hysteresis in magnetization versus dc field scans. These * To whom correspondence should be addressed. Tel: +1-352-392-8314. Fax: +1-352-392-8757. E-mail:
[email protected]. † University of Florida. ‡ Laboratoire of Louis Ne ´ el-CNRS.
10.1021/ic061946y CCC: $37.00 Published on Web 03/21/2007
© 2007 American Chemical Society
hysteresis loops display increasing coercivity with decreasing temperature and increasing field sweep rates, the characteristic signature of superparamagnets. This magnetic behavior of SMMs results from the combination of a large ground spin state (S) with a large and negative Ising (or easy-axis) type of magnetoanisotropy, as measured by the axial zerofield splitting parameter D.1,2 In addition, there is extensive (1) (a) Christou, G.; Gatteschi, D.; Hendrickson, D. N., Sessoli, R. MRS Bull. 2000, 25, 66 and references therein. (b) Aromi, G.; Aubin, S. M. J.; Bolcar, M. A.; Christou, G.; Eppley, H. J.; Folting, K.; Hendrickson, D. N.; Huffman, J. C.; Squire, R. C.; Tsai, H.-L.; Wang, S.; Wemple, M. W. Polyhedron 1998, 17, 3005. (c) Christou, G. Polyhedron 2005, 24, 2065. (2) (a) Sessoli, R.; Gatteschi, D.; Caneschi, A.; Novak, M. A. Nature 1993, 365, 141. (b) Sessoli, R.; Ysai, H. -L.; Schake, A. R.; Wang, S.; Vincent, J. B.; Folting, K.; Gatteschi, D.; Christou, G.; Hendrickson, D. N. J. Am. Chem. Soc. 1993, 115, 1804. (c) Thomas, L.; Lionti, L.; Ballou, R.; Gatteschi, D.; Sessoli, R.; Barbara, B. Nature 1996, 383, 145.
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Mishra et al. bioinorganic interest in 3d metal clusters, and this includes Mn carboxylate clusters3 because of their relevance to elucidating the nature and mechanism of action of the Mn4Ca core of the water oxidizing complex (WOC) of photosynthesis.4 In this paper, we report some recent progress in our ongoing program to develop high-nuclearity, mixed-metal cluster compounds involving 3d and 4f metals. As we shall describe, we have now also extended this work to a mixture of 3d and 5f metals for the first time. Most high-nuclearity, high-spin metal clusters are homometallic Mn species, as was the SMM prototype [Mn12O12(O2CMe)16(H2O)4].2,5 However, several groups,6 as well as our own,7-9 have more recently been exploring heterometallic 3d/4f species as a route to cluster compounds with interesting magnetic properties. Our own work has resulted in a number of new SMMs, namely Mn8Ce,7 Mn11Ln4,8a Mn2Dy2,8b and Fe2Ln29 clusters, although the Mn8Ce SMM actually contains diamagnetic CeIV. In addition, both mixed 3d/4d and 3d/5d SMMs containing Mn are now known.10 The present results were obtained as part of our continuing efforts in Mn/Ce chemistry and have now led to a CeIII2CeIV2MnIII10 product [Ce4Mn10O10(OMe)6(O2CPh)16(NO3)2(MeOH)2(H2O)2] (1) that is the first example of a Mn/Ce cluster to contain CeIII. In addition, our previous results with Mn/CeIV made us wonder whether it might prove possible to extend this chemistry to a mixed 3d transition metal/ actinide cluster, namely a Mn/AcIV (Ac ) actinide) species. Indeed, we report the successful preparation of a ThIV6MnIV10 complex [Th6Mn10O22(OH)2(O2CPh)16(NO3)2(H2O)8] (2), which is the highest nuclearity mixed transition metal/actinide (3) (a) Mukhopadhyay, S.; Mandal, S. K.; Bhaduri, S.; Armstrong, W. H. Chem. ReV. 2004, 104, 3981. (b) Mishra, A.; Wernsdorfer, W.; Abboud, K. A.; Christou, G. Chem. Commun. 2005, 54. (4) (a) Loll, B.; Kern, J.; Saenger, W.; Zouni, A.; Biesiadka, J. Nature 2005, 438, 1040. (b) Ferreira, K. N.; Iverson, T. M.; Maghlaoui, K.; Barber, J.; Iwata, S. Science 2004, 303, 1831. (c) Yachandra, V. K.; Sauer, K.; Klein, M. P. Chem. ReV. 1996, 96, 2927. (5) (a) Miyasaka, H.; Cle´rac, R.; Wernsdorfer, W.; Lecren, L.; Bonhomme, C.; Sugiura, K.; Yamashita, M. A. Angew. Chem., Int. Ed. 2004, 43, 2801. (b) Milios, C. J.; Raptopoulou, C. P.; Terzis, A.; Lloret, F.; Vicente, R.; Perlepes, S. P.; Escuer, A. Angew. Chem., Int. Ed. 2003, 43, 210. (c) Brechin, E. K.; Soler, M.; Davidson, J.; Hendrickson, D. N.; Parsons, S.; Christou, G. Chem. Commun. 2002, 2252. (d) Price, D. J.; Batten, S. R.; Moubaraki B.; Murray, K. S. Chem. Commun. 2002, 762. (e) Sanudo, E. C.; Wernsdorfer, W.; Abboud, K. A.; Christou, G. Inorg. Chem. 2004, 43, 4137. (f) Tasiopoulos, A. J.; Vinslava, A.; Wernsdorfer, W.; Abboud, K. A.; Christou, G. Angew. Chem., Int. Ed. 2004, 43, 2117. (g) Zaleski, C. M.; Depperman, E. C.; Dendrinou-Samara, C.; Alexiou, M.; Kampf, J. W.; Kessissoglou, D. P.; Kirk, M. L.; Pecoraro, V. L. J. Am. Chem. Soc. 2005, 127, 12862. (6) (a) Osa, S.; Kido, T.; Matsumoto, N.; Re, N.; Pochaba, A.; Mrozinski, J. J. Am. Chem. Soc. 2004, 126, 420. (b) Zaleski, C. M.; Depperman, E. C.; Kampf, J. W.; Kirk, M. L.; Pecoraro, V. L. Angew. Chem., Int. Ed. 2004, 43, 3912. (c) Costes, J.-P.; Dahan, F.; Wernsdorfer, W. Inorg. Chem. 2006, 45, 5. (d) Mori, F.; Nyui, T.; Ishida, T.; Nogami,T.; Choi, K.; Nojiri, H. J. Am. Chem. Soc. 2006, 128, 1440. (7) Tasiopoulos, A. J.; Wernsdorfer, W.; Moulton, B.; Zaworotko, M. J.; Christou, G. J. Am. Chem. Soc. 2003, 125, 15274. (8) (a) Mishra, A.; Wernsdorfer, W.; Abboud, K. A.; Christou, G. J. Am. Chem. Soc. 2004, 126, 15648. (b) Mishra, A.; Wernsdorfer, W.; Parsons, S.; Christou, G.; Brechin, E. K. Chem. Commun. 2005, 2086. (9) Murugesu, M.; Mishra, A.; Wernsdorfer, W.; Abboud, K. A.; Christou, G. Polyhedron, 2006, 25, 613. (10) (a) Sokol, J. J.; Hee, A. G.; Long, J. R. J. Am. Chem. Soc. 2002, 124, 7656. (b) Schelter, E. J.; Prosvirin, A. V.; Dunbar, K. R. J. Am. Chem. Soc. 2004, 126, 15004.
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molecular complex to date. We herein describe the syntheses, crystal structures, and magnetic characterization of these species; portions of this work have been previously communicated.11 Experimental Section Syntheses. All manipulations were performed under aerobic conditions using chemicals as received. (NBun4)[Mn4O2(O2CPh)9(H2O)]12 (3) and [Mn3O(O2CPh)6(py)2(H2O)]13 (4) were prepared as previously reported. (NBun4)2Ce(NO3)6. A solution of (NH4)2Ce(NO3)6 (15 g, 27 mmol) in H2O (50 mL) was treated with a solution of NBun4Br (18 g, 55 mmol) in H2O (30 mL) to give a fine orange precipitate. The mixture was stirred for a few more minutes, filtered, and the solid washed with Et2O and dried in vacuo. The yield was 90%. [Ce4Mn10O10(OMe)6(O2CPh)16(NO3)2(MeOH)2(H2O)2] (1). Method A. A solution of complex 3 (1.0 g, 0.62 mmol) in MeCN (20 mL) was treated with solid (NBun4)2Ce(NO3)6 (0.98 g, 0.98 mmol) and was left stirring for 20 min. The resulting brown solution was filtered to remove an off-white precipitate, and the filtrate was then layered with MeOH (10 mL) and left undisturbed at room temperature. After ∼2 weeks, the X-ray quality reddish-brown crystals of 1‚H2O‚4MeOH‚6MeCN that had formed were collected by filtration, washed with Et2O, and dried in vacuo; the yield was 25%. Dried crystals analyzed as 1‚4H2O. Anal. Calcd (Found) for 1‚4H2O (C120H118O62N2Mn10Ce4): C, 39.06 (39.25); H, 3.22 (3.25); N, 0.76 (0.80) %. Selected IR data (KBr, cm-1): 3408(s, br), 1599(s), 1556(s), 1449(w), 1385(s), 1025(w), 716(s), 676(m), 610(m, br), 563(m, br), 437(w). Method B. Complex 1 can also be prepared by treating 4 (1.0 g, 0.92 mmol) in MeCN (20 mL) with solid (NBun4)2Ce(NO3)6 (0.91 g, 0.91 mmol) followed by stirring for 20 min. The subsequent workup was as described in Method A. The product was identified as 1‚4H2O by IR spectroscopy and elemental analysis. The yield was 20%. Anal. Calcd (Found) for 1‚4H2O (C120H118O62N2Mn10Ce4): C, 39.06 (39.21); H, 3.22 (3.20); N, 0.76 (0.78) %. [Th6Mn10O22(OH)2(O2CPh)16(NO3)2(H2O)8] (2). To a slurry of complex 3 (0.25 g, 0.16 mmol) in MeCN/MeOH (20/1 mL) was added solid Th(NO3)4‚3H2O (0.17 g, 0.31 mmol), and the mixture was stirred for 30 min. The resulting brown solution was filtered and the filtrate concentrated by very slow evaporation. Dark redbrown crystals of 2‚10MeCN slowly grew over a few weeks, and these were collected by filtration, washed with acetone, and dried overnight in vacuo; the yield was 20%. Dried material analyzed as fully desolvated. Anal. Calcd (Found) for 2 (C112H98O70N2Mn10Th6): C, 29.67 (29.52); H, 2.18 (2.15); N, 0.62 (0.48) %. Selected IR data (KBr, cm-1): 3392(s, br), 1598(m), 1522(s, br), 1448(w), 1384(s, br), 1025(w), 718(s), 685(m), 615(s, br), 571(w), 482(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 the complexes 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 of reciprocal space revealed a monoclinic cell for 1 and a triclinic cell for 2; the choice of space groups C2/c, and P1h, respectively, were confirmed by the subsequent solution and refinement of the structures. Cell (11) Mishra, A.; Abboud, K. A.; Christou, G. Inorg. Chem. 2006, 45, 2364. (12) Wemple, M. W.; Tsai, H.-L.; Wang, S.; Claude, J.-P.; Streib, W. E.; Huffman, J. C.; Hendrickson, D. N.; Christou, G. Inorg. Chem. 1996, 35, 6450. (13) Vincent, J. B.; Chang, H. R.; Folting, K.; Huffman, J. C.; Christou, G.; Hendrickson, D. N. J. Am. Chem. Soc. 1987, 109, 5703.
High-Nuclearity Ce/Mn and Th/Mn Cluster Chemistry Table 1. Crystallographic Data for 1‚H2O‚4MeOH‚6MeCN and 2‚10MeCN
formula fw, g/mol space group a, Å b, Å c, Å R, deg β, deg γ, deg V, Å3 Z T, K radiation, Åa Fcalc, g/cm3 µ, mm-1 R1b,c wR2d
1
2
C136H146N8O63Mn10Ce4 4010 C2/c 32.408(2) 16.9687(11) 27.6545(17) 90 95.942(2) 90 15126.2(17) 4 173(2) 0.71073 1.750 2.074 0.0805 0.1866
C132H128N12O70Mn10Th6 4944 P1h 15.0752(13) 16.0141(14) 17.8295(15) 80.900(2) 72.585(2) 66.351(2) 3758.5(6) 1 173(2) 0.71073 2.183 6.819 0.0707 0.1647
a Graphite monochromator. b I > 2σ(I). c R1 ) 100∑(||F | - |F ||)/∑|F |. o c o wR2 ) 100[∑[w(Fo2 - Fc2)2]/∑[w(Fo2)2]]1/2, w ) 1/[σ2(Fo2) + [(ap)2 +bp], where p ) [max (Fo2, O) + 2Fc2]/3.
d
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 2σ(I) to yield R1 and wR2 of 8.05% and 18.66%, respectively. For 2‚10MeCN, the asymmetric unit consists of half the cluster and five MeCN solvent molecules of crystallization. The latter were disordered and could not be modeled properly, and the program SQUEEZE14b was used to calculate the solvent disorder area and remove its contribution to the overall intensity data. A total of 791 parameters were included in the structure refinement on F2 using 16 874 reflections with I > 2σ(I) to yield R1 and wR2 of 7.07% and 16.47%, respectively. Unit cell data and details of the structure refinements for 1‚H2O‚ 4MeOH‚6MeCN and 2‚10MeCN are listed in Table 1. Other Studies. Infrared spectra were recorded in the solid state (KBr pellets) on a Nicolet Nexus 670 FTIR spectrometer in the 400-4000 cm-1 range. Elemental analyses (C, H, and N) were performed by the in-house facilities of the University of Florida Chemistry Department. Variable-temperature dc and ac magnetic susceptibility data were collected at the University of Florida using a Quantum Design MPMS-XL SQUID susceptometer equipped (14) (a) Sheldrick, G. M. SHELXTL6; Bruker-AXS: Madison, WI, 2000. (b) van der Sluis, P.; Spek, A. L. Acta Crystallogr. 1990, A46, 194. (c) Spek, A. L. Acta Crystallogr. 1990, A46, C34.
with a 7 T magnet and operating in the 1.8-300 K range. Samples were embedded in solid eicosane to prevent torquing. Magnetization vs field and temperature data were fit using the program MAGNET.15 Pascal’s constants were used to estimate the diamagnetic correction, which was subtracted from the experimental susceptibility to give the molar paramagnetic susceptibility (χM). Studies at ultralow temperatures (1.8 K then reveal clear hysteresis in dc magnetization sweeps assignable to an SMM with blocking temperatures of at least ∼0.6 K or more. Nor can the answer be due to whether the sample was used wet with mother liquor or first dried. We have certainly seen in the past that the latter sometimes causes significant differences in the relaxation barrier,26a,29,30 for example, wet crystals showing no χM′′ signals down to 1.8 K but dried solid showing strong ones at >1.8 K.29 For complex 1, in contrast, wet and dried samples give essentially identical χM′′ signals, so it is valid to compare the ac data in Figure 7 with the single-crystal data in Figure 9. Thus, we cannot offer an unequivocal explanation of the origin of the χM′′ signals, except to state the obvious that it must be due to a combination of factors such as intermolecular interactions, phonon bottlenecks, and perhaps other contributions. Note that the groups involved in the hydrogen bonds between neighboring molecules are attached to metal ions and thus would not be expected to be lost on drying, as confirmed by the elemental analysis of dried material. We thus do not anticipate any significant change to the intermolecular hydrogen bonds on drying. This is consistent with the observation that wet and dried samples give essentially identical χM′′ signals. In any case, much more important is the overall conclusion from the combined results of this study that, as we have stated before, the appearance of χM′′ signals is necessary but not sufficient proof of a SMM. Complex 1 is now another example of this important caveat.27 (28) Petrukhina, M. A.; Sergienko, V. S.; Sadikov, G. G.; Tat’yanina, I. V.; Torchenkova, E. A. Koord. Khim. (Russ.) (Coord. Chem.) 1990, 16, 354. (29) Boskovic, C.; Brechin, E. K.; Streib, W. E.; Folting, K.; Bollinger, J. C.; Hendrickson, D. N.; Christou, G. J. Am. Chem. Soc. 2002, 124, 3725. (30) (a) Tasiopoulos, A. J.; Wernsdorfer, W.; Abboud, K. A.; Christou, G. Angew. Chem., Int. Ed. 2004, 43, 6338. (b) Tasiopoulos, A. J.; Wernsdorfer, W.; Abboud, K. A.; Christou, G. Inorg. Chem. 2005, 44, 6324.
High-Nuclearity Ce/Mn and Th/Mn Cluster Chemistry
Acknowledgment. We thank the National Science Foundation for support of this work.
10MeCN. This material is available free of charge via the Internet at http://pubs.acs.org.
Supporting Information Available: X-ray crystallographic data in CIF format for complexes 1‚H2O‚4MeOH‚6MeCN and 2‚
IC061946Y
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