CRYSTAL GROWTH & DESIGN
Testing the High Spin MnII9WV6 Cluster as Building Block for Three-Dimensional Coordination Networks
2008 VOL. 8, NO. 10 3817–3821
Robert Podgajny,*,† Wojciech Nitek,† Michał Rams,‡ and Barbara Sieklucka† Faculty of Chemistry, Jagiellonian UniVersity, Ingardena 3, 30-060 Krako´w, Poland, and M. Smoluchowski Institute of Physics, Jagiellonian UniVersity, Reymonta 4, 30-059 Krako´w, Poland ReceiVed May 6, 2008; ReVised Manuscript ReceiVed July 4, 2008
ABSTRACT: Pentadecanuclear high spin cyano-bridged {M′II9M′′V6(CN)48(solv)24} (M′ ) 3d metal ions; M′′ ) Mo, W; solv ) H2O, alcohol) clusters are considered as building blocks for three-dimensional open networks. Self-assembly of MnII9WV6 clusters (S ) 39/2) with 4,4′-bipyridine leads to their organization into an organic-inorganic hybrid coordination network {MnII9(4,4′bpy)4[WV(CN)8]6(EtOH)12(H2O)4} · 10EtOH 1 (System, triclinic; space group: P1j, a ) 17.1569(2) Å, b ) 17.3835(2) Å, c ) 19.2530(2) Å, R ) 103.5520(10)°, β ) 115.3950(10)°, γ ) 98.3060(10)°, Z ) 1). The clusters are connected through 4,4′-bpy spacers into a two-dimensional square-grid coordination framework extended in the ab crystallographic plane with the smallest intercluster separation along the a (Mn · · · W ) 7.12 Å) and b (Mn · · · W ) 7.15 Å) directions significantly lower than that along the c crystallographic direction (Mn · · · W ) 8.64 Å). Direct current magnetic measurements suggest strong dominance of intracluster antiferromagnetic MnII-WV coupling over a very weak intercluster antiferromagnetic interaction.
During the recent decade an effective approach has been successfully implemented in the synthesis of functional materials from single-metal-ion based coordination clusters. The key features of the building blocks for the multifunctionality of the resulting coordination network are intrinsic properties of simple molecules involved (e.g., reactivity, electronic spin, redox potentials, optical properties) along with their geometric arrangement. Of particular interest are the coordination clusters with Lewis acid coordination sites as well as Lewis base donor atoms offering the opportunity to create the well defined target three-dimensional (3D) coordination networks.1 In this context the investigation on the structural organization of high nuclearity octacyanometalate-based clusters into extended coordination architectures provide a new attractive path forward in developing multifunctionality of such systems. The use of octacyanometalates of Mo, Nb, and W together with cationic complexes and organic molecules (chelating ligands, spacers, cations) as building blocks appears to be of importance in exploring possible synergies between magnetic coupling2 and physicochemical properties associated with their porous natures, guest sorption/desorption,3 optical MMCT,4 and physically modulated structural or/and interstate equilibria.5 The reasonable choice for further studies is a class of pentadecanuclear sixcapped body-centered cube {M′II9M′′V6(CN)48(solv)24} (M′ ) Mn(II), Co(II), Ni(II); M′′ ) Mo, W, solv - MeOH, EtOH, H2O) clusters formed in H2O/organic media.6 These clusters are characterized by well pronounced magnetic interaction of metal centers through CN- bridges and high spin ground states: JMnM′′ < 0 and S ) 39/2 for Mn(II),6a-c JCoM′′ < 0 and S ) 21/2 for Co(II),6d and JNiM′′ > 0 and S ) 12 for Ni(II).6e-g For the Mn9Mo6 cluster, the application of density-functional theory (DFT) methods to dinuclear [(NC)7MoV(µ-CN)-MnIIL5]n- (L ) CN-, solv) fragments allowed to estimate the values of JMnMo exchange parameters to be about -20 cm-1 or about -12 cm-1, depending on the position of the Mo-CN-Mn linkage in the
[MoV(CN)8]3- dodecahedron.6c For Ni9M′′6 clusters the JNiM′′ of about 16 cm-1 was estimated using the extrapolation methods.6e For{CoII9MV6},6dbrokensymmetry{NiII9MV6(2,2′-bpy)8},6e,f and trimetallic mixed-metal {CoII9WV5ReV} clusters6h some evidence of spin relaxation were reported. Acting as the remarkably high spin nodes of the coordination network, M′II9M′′V6 clusters can be considered as magnetic units of defined size that may offer new possibilities for quantum computing applications. The molecular structure of M′II9M′′V6 clusters represent six octahedrally arranged [M′′(CN)8]3- moieties forming one cyanobridge to the central M′(II) cation and four cyano-bridges toward peripheral M′(II) moieties located at the vertexes of a cube (Figure 1). The key structural features of the solvated cluster are (i) eight pseudo-octahedral M′(II) moieties, each with the triad of facarranged labile solvent molecules pointing out of the cyano-bridged skeleton and (ii) six octacyanometalate(V) moieties, each with three basic nitrogen ends of CN- ligands. In both cases, one observes well defined, localized, and oriented regions were the extension toward the polymeric architecture may occur, for example, through organic bridges from M′(II) centers and through cyano-bridges from M′′(V) centers. These clusters appear to be qualitatiVely (in respect to their symmetry) equivalent to the structural motifs observed in traditional minerals (fluorite CaF2 net,1b sodalite Na8Cl2[Al6Si6O24] β-cage7), as well as hybrid inorganic solid phases (e.g., [Re6Q8(CN)6]4- (Q ) S, Se, Te) anions in bimetallic porous networks8), and may be considered as potential building blocks for 3D coordination networks. The aim of the present study is to test the applicability of solvated MnII9WV6 clusters in the formation of high dimensional hybrid inorganic-organic coordination networks, which is the first step toward networks with tuned intercluster separation and solvent cavity size. Herein, we report the hybrid inorganicorganic two-dimensional (2D) network {MnII9(4,4′-bpy)4[WV(CN)8]6(EtOH)12(H2O)4} · 10EtOH 1, presenting the first example of self-assembly between high spin MnII9WV6 clusters and the linear rigid spacer 4,4′-bpy.
* To whom correspondence should be addressed. E-mail: podgajny@ chemia.uj.edu.pl. † Faculty of Chemistry. ‡ M. Smoluchowski Institute of Physics.
Materials. Mn (ClO4)2 · 6H2O and 4,4′-bipyridine were purchased from commercial sources (Aldrich, Idalia) and used without further
Introduction
Experimental Section II
10.1021/cg800470e CCC: $40.75 2008 American Chemical Society Published on Web 09/05/2008
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Podgajny et al. Table 1. Crystal Data and Structure Refinement for 1 formula T λ system space group a/Å b/Å c/Å R/deg β/deg γ/deg V/Å3 Z Dcalc/Mg/m3 µ/mm-1 crystal size F(000) θ range refinement method R1 [I > 2σ(I)] wR2 G(F2)
Figure 1. Polyhedral representation of the {M′9M′′6(CN)48(solv)24} cluster.6 Six [M′′V(CN)8]3- moieties (blue) are coordinated to one central [M′II(NC)6]4- moiety and eight peripheral fac-[M′II(CN)3(solv)3]- (pink-violet) moieties. The eight triads of atoms of substitutable coordinating solvent molecules (green balls) create a basis of possible built-up directions toward the extended organic-inorganic hybrid network. C, small blue balls; N, small pink balls; C-N bonds of CN--ligands, dark violet sticks. purification. Na3[WV(CN)8] · 4H2O9 was synthesized according to the literature procedure. Synthesis of 1. A 0.1 mmol quantity (53.3 mg) of Na3[WV(CN)8] · 4H2O together with 0.15 mmol (54.2 mg) of Mn(ClO4)2 · 6H2O were dissolved in 5 mL of ethanol, and the resulting pale brown solution I was stirred for 30 min. A 0.75 mmol quantity (177 mg) of 4,4-bpy was dissolved in 5 mL of ethanol to give solution II. Solution I (ca. 1 mL) and solution II (ca. 1 mL) were gently transferred into two separate arms of 10 mL H-tubes and finally the ethanol was layered over each solution to connect both arms. The H-tubes were placed in the dark and left for crystallization. After 1 month very small brown crystals started to appear in the Mn/W arm of an H-tube. The monocrystalline objects suitable for X-ray characterization were developed during another month of crystal growth. The composition of 1, {MnII9(4,4′bpy)4[WV(CN)8]6(EtOH)12(H2O)4} · 10EtOH (C132H172Mn9N56O26W6, Mmol ) 4554 g · mol-1) was determined based on the X-ray diffraction measurement. The careful washing of crystals with ethanol maintains their monocrystalline form, while the removal of solvent leads immediately to the breakdown of the crystals producing powder 1a. A freshly separated brown solid sample 1a (Yield: 7.0(2) mg) was characterized by means of elementary analysis and IR spectroscopy. Found: C, 28.2%, H 2.1%, N 19.4%. Calcd for C96H100Mn9N56O26W6 (equivalent to Mn6W9(bpy)4(H2O)22(EtOH)4 composition, Mmol ) 4052 g · mol-1): C, 28.5%; H, 2.5%; N, 19.4%. IR (KBr pellets) in cm-1: ν(OH) 3424s(br); ν(CN), 2198w(sh), 2165m, 2140w(sh); δ(H2O) 1609vs; 4,4′-bpy, (ArCdC) 1551w, 1453w, 1414m, 1323vw; γ(ArCH in-plane), ring breathing, ring deformation, γ(ArCH out-of-plane), 1221w, 1067m, 1047w, 1008m, 811m, 630m; Coordination, 571vw, 466m(br). The composition and IR spectrum of 1a suggest the that during drying the WV-CN-Mn and Mn-(4,4′-bpy)-Mn coordination linkages are maintained, while some of the EtOH molecules are replaces by H2O. The effective decrease in molar mass on going from 1 to 1a allow to estimate the real amount of wet magnetically active sample 1. Structure Solution and Refinement. The single-crystal diffraction data for 1 were collected on a Nonius Kappa CCD equipped Mo KR radiation source and graphite monochromator at 100 K (flash cooling mounting over LN2). The space group was determined using the ABSEN10a program. The structures were solved by the Patterson method using the program SHELXS-97.10b The refinement and further calculation for all compounds were carried out using SHELXL-97.10c The non-H atoms except of crystallization ethanol carbon and oxygen
C132H32Mn9N56O26W6 100(2) K 0.71073 Å triclinic P1j 17.1569(2) 17.3835(2) 19.2530(2) 103.5520(10) 115.3950(10) 98.3060(10) 4842.74(9) 2 1.51 8.297 0.25 × 0.18 × 0.10 mm3 2093 1.24 to 29.92°. full-matrix least-squares on F2 0.0588 0.1867 1.065
atoms were refined anisotropically, using weighted full-matrix leastsquares on F2. All hydrogen atoms joined to carbon atoms in 4,4′-bpy molecules were positioned with idealized geometry and refined using a riding model, with Uiso(H) fixed at 1.2Ueq(C). H atoms in water molecules and ethanol molecules were not included because of disorder present outside of the coordination skeleton. The selected crystallographic data for the studied compounds are shown in Table 1. Structural artworks were prepared using VESTA11 and Mercury 1.4.1 software. Physical Techniques. Elemental analyses (C, H, N) were performed using an EuroEA EuroVector elemental analyzer. Infrared spectra were measured in KBr pellets between 4000 and 400 cm-1 using a Bruker EQUINOX 55 FT-IR spectrometer. Magnetic measurements were performed using Quantum Design SQUID magnetometer MPMS-XL. The sample of 1 was washed from the mother liquor, immersed in 96% ethanol and closed in a glass tube. Direct current measurement were carried out only below 150 K, to ensure that the sample was frozen. The diamagnetic signal of the components of solid 1, as well as of 28 mg EtOH, was subtracted. The mass of the magnetically active sample of 1 was estimated to be 7.7(3) mg (see Synthesis of 1). Alternating current (ac) susceptibility measurements were made at Hac ) 3 Oe, at frequencies 1-1000 Hz, down to 1.8 K.
Result and Discussion The crystal structure of 1 consists of 2D square-grid layers formed by MnII9WV6 clusters joined by pairs of 4,4′-bpy linkers coordinated to the manganese(II) centers (Figure 2). The layers are oriented parallel to the ab crystallographic plane. The selected distances parameters are presented in Supporting Information, Table S1. The molecular structure of the Mn9W6 unit in 1 resembles a cyano-bridged core structure observed for the discrete clusters (Supporting Information, Figure S1).6 Continuous Shape Measure analysis12 indicates that the [W1(CN)8] and [W2(CN)8] complexes have geometry very close to the intermediate SAPR-8/DD-8 polyhedron, while [W3(CN)8] is much closer to the dodecahedral geometry (Supporting Information, Table S2). Figure 3 shows a representative fragment of the cluster exhibiting the coordination spheres of Mn(II) centers. The central Mn1 ion coordinates six N ends of the cyano-bridges in minimally elongated octahedral geometry along the W3-Mn1-W3a direction. The peripheral Mn(II) centers are represented by two sets of four sites Mn2, Mn3, Mn4, and Mn5. All of them coordinate three N atoms of the CN- bridges arranged in fac-geometry. Their pseudo-octahedral coordination spheres are completed by different sets of ligands: Mn2, one nitrogen atom of 4,4′-bpy ligand and two oxygen
MnII9WV6 Clusters Organized into a Hybrid Network
Crystal Growth & Design, Vol. 8, No. 10, 2008 3819
Figure 2. Crystal structure of 1: a fragment of a 2D 4,4′-bipyridine-bridged Mn9W6(CN)48 layer; (b) Colors: [WV(CN)8]3- polyhedra (blue), central [MnII(NC)6]4- and peripheral fac-[MII(CN)3(solv)3]- polyhedra (pink-violet), 4,4′-bipyridine (green balls and sticks), C-N bonds of CN--ligands (dark violet sticks). Hydrogen atoms, EtOH and H2O ligands molecules were omitted for clarity.
Figure 3. Crystal structure of 1: the coordination spheres for the Mn1-Mn5 centers with atom labeling scheme. Colors: [WV(CN)8] units (blue), Mn(II) centers (pink), 4,4′-bipyridine (green), EtOH and H2O ligands (red). Terminal cyano-ligands, crystallization EtOH, crystallization H2O molecules, and hydrogen atoms were omitted for clarity.
atoms of H2O and EtOH solvent molecules; Mn3, one nitrogen atom of 4,4′-bpy ligand and two oxygen atom of EtOH molecule; Mn4, two nitrogen atoms of different 4,4′-bpy ligands and one oxygen atom EtOH molecule; Mn5, three oxygen atoms of two EtOH and one H2O molecules. The Mn-Owater,EtOH (mean value 2.186 Å) and Mn-Nbpy (mean value 2.286 Å) distances are consistent with those reported for the relevant coordination assemblies.2b-e,13 The 4,4′-bpy ligands exhibit characteristic internal twisting of about 30-40° between the planes, the aromatic rings being oriented diagonally to the relevant axes of Mn(II) pseudooctahedra. The Mn-(4,4′bpy)-Mn linkages are characterized by Mn · · · Mn distances as follows: Mn3 · · · Mn4 of 11.64 Å along the a axis and Mn2 · · · Mn4 of 11.64 Å along the b axis. Intralayer and interlayer hydrogen bonding involving nitrogen atoms of terminal CN- ligands and oxygen atoms of crystallization
Figure 4. Closest contacts between the Mn9W6(CN)48 units: (a) intralayer, along the a crystallographic axis, including symmetry related MnII-(4,4′-bpy)-MnII linkages and MnII-Owater-H · · · N-C-WV hydrogen bondings; O2 · · · N28 ) 2.76 Å (qualitatively representative for the b crystallographic direction as well); (b) interlayer, along the c crystallographic direction, realized through two symmetry related MnII-OEtOH-H · · · OEtOH-H · · · N-C-WV hydrogen bonding systems; O41a · · · O1a ) 2.71 Å, O1a · · · N36 ) 2.83 Å. The atoms directly involved in the formation of inter-unit non-covalent contacts are depicted in a dark gray color.
solvent molecules co-stabilize the 3D architecture of 1 (Figure 4). The closest contacts between Mn9W6 units in 1 may be expressed by the Mn · · · W and Mn · · · Mn through-space distances: Mn2 · · · W2 of 7.12 Å and Mn2 · · · Mn2 of 8.34 Å along the a axis, Mn5 · · · W1 of 7.15 Å and Mn5 · · · Mn5 of 8.13 Å along the b axis, Mn4 · · · W3 of 8.64 Å and Mn4 · · · Mn4 of 8.98 Å along the c axis. The smallest intercluster separations along
3820 Crystal Growth & Design, Vol. 8, No. 10, 2008
Podgajny et al.
magnetic Mn(II)-W(V) intracluster magnetic coupling over a weak intercluster antiferromagnetic interaction starting to operate at very low temperature. Conclusions
Figure 5. Magnetic characteristics for 1: χT(T) dependence (Hdc ) 1 kOe) and (inset) M(H) dependence (T ) 1.8 K) (•, experimental data; solid line, calculated for S ) 39/2 and g ) 2). Dotted lines mark the theoretical limits of χT for the ferrimagnetic Mn9W6 cluster with g ) 2. Abbreviations: LT, low temperature; HT, high temperature.
the a and b axes are very close to those found in solvated clusters {M′9M′′6(CN)48(solv)24}6a,b,d,h and significantly lower than 7.9 Å found for {Ni9M6(CN)48(2,2′-bpy)8(solv)8},6f,g while the relevant separation along the c axis of 8.64 Å is remarkably greater compared to the former ones. The supramolecular arrangement of 1 results in the 1D slit-like channels of approximate dimensions 2.5 × 7.5 Å weaving along the a and c crystallographic directions, occupied by disordered solvent molecules (Supporting Information, Figure S2). The IR spectrum of 1a residue (freshly dried sample of 1, see Experimental Section) in the ν(CN) region exhibits three distinguishable bands 2198w(sh), 2165m, and 2140w(sh) cm-1 confirming the presence of bridging WV-CN-Mn and terminal WV-CN coordination arrangements.2b-e,6,14 The region characteristic for vibrations of organic molecules exhibits the set of bands assignable to the C-H in-plane or out-of-plane bend, ring breathing, and ring deformation absorption of 4,4′-bpy ligands.15 The band located at 630 cm-1 is consistent with the presence of bridging modes of 4,4′-bpy.16 Magnetic data were recorded for a solid crystalline sample immersed in 96% EtOH (see Experimental Section). The high temperature limit of χT measured at 150 K equals 43(2) cm3 · K · mol-1, which is close to 41.2 cm3 · K · mol-1 expected for uncoupled 9 Mn(II) spins S ) 5/2 and 6 W(V) spins S ) 1/2 assuming g ) 2 at 300 K (Figure 5). The significant increase of the χT signal measured at H ) 1 kOe is observed with decreasing temperature. The maximum value of 185 cm3 · K · mol-1 is reached at 7 K; then, the χT product decreases down to 160 cm3 · K · mol-1, probably because of the onset of antiferromagnetic intermolecular interactions. This maximum value is slightly lower than the low temperature limit of χT ) 200 cm3 · K · mol-1 expected for the isolated spin S ) 39/2. Almost the same behavior is observed using the χac data measured at Hac ) 3 Oe. The M(H) curve measured at 1.8 K tends to saturate reaching the value of 38(2) Nβ at 50 kOe (Figure 5 inset). The relevant Brillouin curve for spin S ) 39/2 and g ) 2 reproduces reasonably the experimental data. Neither long-range magnetic ordering nor magnetic relaxation behavior is observed in the χ′ and χ′′ ac susceptibility measurement down to 1.8 K. The observed trends in χT(T) and M(H) dependences for 1 are generally comparable to those measured for {MnII9[WV(CN)8]6 · 24EtOH} · 12EtOH containing solvated MnII9WV6 clusters6a and indicate the dominance of antiferro-
Taking advantage of the structural features of solvated {Mn6W9(CN)48} clusters, we demonstrate for the first time their organization into an extended inorganic-organic hybrid network. The 2D square-grid coordination arrangement of the resulting network and its stability at ambient condition seems to be somehow controlled by a hydrogen bonding network. However, we recognize 1 as an extremely attractive material for further study on the structural ordering of nano-sized highspin species. We believe the presented results are an important step toward molecular materials with spin state, intercluster separation, and pore size tunable by the properties of the 3d metallic center, as well as by the nature of the intercluster molecular bridge. Along this line, studies on the application of the anisotropic 3d metal ions along with the photoreactive and/ or structurally flexible organic linkers to achieve dynamic functional solids sensitive for external stimulation are in progress. Acknowledgment. The study has been partially supported by the EC within its NoE project MAGMANet, contract No. NMP-3-CT-2005-515767. Supporting Information Available: Crystallographic information in CIF format for 1, Platon Check-cif including our comments, Figures S1 and S2 presenting displacement ellipsoids and example 3D view of the structure, Details of Continuous Shape Measure analysis. This material is available free of charge via the Internet at http://pubs.acs.org.
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MnII9WV6 Clusters Organized into a Hybrid Network
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CG800470E
