Synthesis, crystal structures, and magnetic properties of two three-dimensional octacyanotungstate(IV)-based bimetallic frameworks with 4,4′-bipyridine dioxide (4,4′-dpdo)
Tóm tắt
The reaction of [HN(n-C4H9)3]3[WV (CN)8]·4H2O, 4,4′-bipyridine dioxide(4,4′-dpdo), and MnCl2·4H2O or CuCl2·2H2O gives two new three-dimensional octacyanometalate-based bimetallic assemblies, {[Mn2 (4,4′-dpdo)(H2O)4] [WIV (CN)8]{·6H2O (1) and {[Cu2(4,4′-dpdo)(H2O)][W(CN)8]{·CH3OH·H2O (2). Compound 1 crystallizes in the orthorhombic system, space group P21212 with cell constants α=10.397(2) Å, b=11.321(2) Å, c=12.295(3) Å and Z=2, whereas 2 crystallizes in the monoclinic system, space group P21/c with cell constants a=13.038(3) Å, b=13.784(3) Å, c=13.225(3) Å, β=93.44(3)° and Z=4. In complex 1, each [WIV (CN)8]4− unit with a square antiprismatic geometry is connected to four Mn2 dimers through four bridging CN− ions forming wavelike alternating-W-Mn2-W-Mn2- layers, which are further linked through 4,4′-dpdo ligands coordinated to the Mn ions into a three-dimensional open framework. In complex 2, each [WIV (CN)8]4− ion still adopts a square antiprismatic geometry, whereas it bonds to seven copper ions through seven CN− ions leading to cage-like undulate layers further bridged by 4,4′-dpdo ligands into a three-dimensional network. Due to the bridging role of the long rigid 4,4′-dpdo ligand, there exist plenty of large cavities in the open frameworks of complexes 1 and 2 occupied by solvent clusters containing H2O or CH3OH molecules. To our knowledge, it is noted that 4,4′-dpdo displays a μ-4,4,4′,4′ mode, which was first experimentally observed, although predicted before. Magnetic studies show that complex 1 displays an antiferromagnetic coupling between MnII ions, while complex 2 exhibits a weak ferromagnetic interaction between CuII ions.
Tài liệu tham khảo
Sieklucka B, Szklarzewicz J, Kemp T J, Errington W. X-ray evidence of CN bridging in bimetallic complexes based on [M(CN)8]4− (M = Mo,W). The crystal structure of {[Mn(bpy)2]2(μ-NC)2[Mo(CN)6]2(μ-CN)2[Mn(bpy)2]2}·8H2O. Inorg Chem, 2000, 39(22): 5156–5158
Rombaut G, Verelst M, Golhen S, Ouahab L, Mathonière C, Kahn O. Structural and photomagnetic studies of two compounds in the system Cu2+/Mo(CN)8 4−: From trinuclear molecule to infinite network. Inorg Chem, 2001, 40(6): 1151–1159
Bonadio F, Gross M, Stoeckli-Evans H, Decurtins S. High-spin molecules: Synthesis, X-ray characterization, and magnetic behavior of two new cyano-bridged NiII 9MoV 6 and NiII 9WV 6 clusters with a S = 12 ground state. Inorg Chem, 2002, 41(22): 5891–5896
Podgajny R, Korzeniak T, Bałanda M, Wasiutyski T, Errington W, Kemp T J, Alcock N W, Sieklucka B. 2-D soft ferromagnet based on [WV(CN)8]3− and CuII with a Tc of 34 K. Chem Commun, 2002, 2(10): 1138–1139
Li D F, Zheng L M, Wang X Y, Huang J, Gao S, Tang W X. [Cu(tn)]3[W(CN)8]2·3H2O and [Cu(pn)]3[W(CN)8]2·3H2O: Two novel Cu(II)-W(V) cyano-bridged two-dimensional coordination polymers with metamagnetism. Chem Mater, 2003, 15(10): 2094–2098
Podgajny R, Korzeniak T, Stadnicka K, Dromzée Y, Alcock N W, Errington W, Kruczała K, Bałanda M, Kemp T J, Verdaguer M, Sieklucka B. Coordination polymers based on octacyanometalates (IV,V) (M=Mo, W) and aliphatic polyamine copper(II) tectons with [N3] donor atom sets. Dalton Trans, 2003, 3(17): 3458–3468
Arimoto Y, Ohkoshi S I, Zhong Z J, Seino H, Mizobe Y, Hashimoto K. Photoinduced magnetization in a two-dimensional cobalt octacyano-tungstate. J Am Chem Soc, 2003, 125(31): 9240–9241
Li D F, Zheng L, Zhang Y, Huang J, Gao S, Tang W. Coexistence of long-range ferromagnetic ordering and glassy behavior in one-dimensional bimetallic cyano-bridged polymers. Inorg Chem, 2003, 42(19): 6123–6129
Herrera J M, Bleuzen A, Dromzée Y, Julve M, Lloret F, Verdaguer M. Crystal structures and magnetic properties of two octacyanotungstate (IV) and (V)-cobalt(II) three-dimensional bimetallic frameworks. Inorg Chem, 2003, 42(22): 7052–7059
Ohkoshi S, Arimoto Y, Hozumi T, Seino H, Mizobe Y, Hashimoto K. Two-dimensional metamagnet composed of cyano-bridged CuII-WV bi-metallic assembly. Chem Commun, 2003, 3(22): 2772–2773
Hozumi T, Ohkoshi S, Arimoto Y, Seino H, Mizobe Y, Hashimoto K. Cooling-rate dependent ferromagnetism in a two-dimensional cyano-bridged Sm(III)-W(V) Complex. J Phys Chem B, 2003, 107(42): 11571–11574
Kashiwagi T, Ohkoshi S, Seino H, Mizobe Y, Hashimoto K. Manganese (II) octacyanotungstate(V)-based magnet containing a non-coordinated aromatic molecule. J Am Chem Soc, 2004, 126(16): 5024–5025
Pradhan R, Desplanches C, Guionneau P, Sutter J P. Octadecanuclear cluster or 1D polymer with [{ML}2Nb(CN)8]n motifs as a function of {ML} (M=Ni(II), n=6; M=Mn(II), n=∞; L=macrocycle). Inorg Chem, 2003, 42(21): 6607–6609
Kou H Z, Ni Z H, Zhou B C, Wang R J. A cyano-bridged molecule-based magnet containing manganese(III) schiff base and octacyano-tungstate (II) building blocks. Inorg Chem Commun, 2004, 7(10): 1150–1153
Mathonière C, Podgajny R, Guionneau P, Labrugere C, Sieklucka B. Photomagnetism in cyano-bridged hexanuclear clusters [MnII(bpy)2]4 [MIV(CN)8]2·xH2O (M=Mo, x=14, and M=W, x=9). Chem Mater, 2005, 17: 442–449
Withers J R, Li D F, Triplet J, Ruschman C, Parkin S, Wang G, Yee G T, Holmes S M. A two-dimensional octacyanomolybdate(V)-based ferrimagnet: {[MnII(DMF)4]3[MoV(CN)8]2}n. Inorg Chem, 2006, 45(11): 4307–4309
Wang Z X, Zhang P, Shen X F, Song Y, You X Z, Hashimoto K. Syntheses, structures, and properties of two three-dimensional octa-cyanometalate-based polymers: Cs2Cu3[W(CN)8]2·4NH3·4H2O and Cu2[Mo(CN)8]·8NH3. Cryst Growth Des, 2006, 6(11): 2457–2462
You Y S, Yoon J H, Lim J H, Kim H C, Hong C S. Cyano-bridged CuII-MV (M=Mo, W) bimetallic layered complexes exhibiting novel honeycomblike structures. Inorg Chem, 2005, 44(20): 7063–7069
Visinescu D, Desplanches C, Imaz I, Bahers V, Pradhan R, Villamena F A, Guionneau P, Sutter J P. Evidence for increased exchange in-teractions with 5d compared to 4d metal ions. Experimental and theoretical insights into the ferromagnetic interactions of a series of trinuclear [{M(CN)8}3−/NiII] compounds (M=MoV or WV). J Am Chem Soc, 2006, 128(31): 10202–10212
Hozumi T, Hashimoto K, Ohkoshi S. Electrochemical synthesis, crystal structure, and photomagnetic properties of a three-dimensional cyano-bridged copper-molybdenum complex. J Am Chem Soc, 2005, 127(11): 3864–3869
Zhong Z J, Seino H, Mizobe Y, Hidai M, Verdaguer M, Ohkoshi S, Hashimoto K. Crystal structure and magnetic properties of an octa-cyanometalate-based three-dimensional tungstate(V)-manganese(II) bimetallic assembly. Inorg Chem, 2000, 39(22): 5095–5101
Entley W R, Girolami G S. High-temperature molecular magnets based on cyanovanadate building blocks: Spontaneous magnetization at 230 K. Science, 1995, 268: 397–400
Ferlay S, Mallah T, Ouahès R, Veillet P, Verdaguer M. A room-temperature organometallic magnet based on prussian blue. Nature, 1995, 378: 701–703
Beltran L M C, Long J R. Directed assembly of metal-cyanide cluster magnets. Acc Chem Res, 2005, 38(4): 325–334
Sato O. Optically switchable molecular solids: Photoinduced spin-crossover, photochromism, and photoinduced magnetization. Acc Chem Res, 2003, 36(9): 692–700
Sra A K, Andruh M, Kahn O, Golhen S, Ouahab L, Yakhmi J V. A mixed-valence and mixed-spin molecular magnetic material: [MnIII]6 [MoIII(CN)7][MoIV(CN)8]2 - 19.5·H2O. Angew Chem Int Ed, 1999, 38(17): 2606–2609
Ohba M, Usuki N, Fukita N, Ökawa H. Structure and magnetic properties of one-dimensional PPh4[Ni(pn)2][M(CN)6]·H2O (M=Fe, Cr, Co) bimetallic assemblies. Inorg Chem, 1998, 37(13): 3349–3354
Kou H Z, Tang J K, Liao D Z, Gao S, Cheng P, Jiang Z H, Yan S P, Wang G L, Chansou B, Tuchagues J. Crystal structures and magnetic properties of new cyano-bridged two-dimensional grid-like bimetallic assemblies [Ni(tn)2]2[Cr(CN)5((NO))OH·H2O and [Ni(tn)2]2[Co(CN)6] NO3·2H2O (tn=1,3-Propanediamine). Inorg Chem, 2001, 40(19): 4839–4844
Song Y, Zhang P, Ren X M, Shen X F, Li Y Z, You X Z. Octa-cyanometallate-based single-molecule magnets: CoII 9MV 6 (M=W, Mo). J Am Chem Soc, 2005, 127(11): 3708–3709
Li D, Zheng L, Zhang Y, Huang J, Gao S, Tang W. Coexistence of long-range ferromagnetic ordering and glassy behavior in one-dimensional bimetallic cyano-bridged polymers. Inorg Chem, 2003, 42(19): 6123–6129
Li D, Gao S, Zheng L, Sun W, Okamura T, Ueyama N, Tang W. A novel Cu(II)-W(V) bimetallic assembly magnet {[Cu(en)2]3[W(CN)8]2·H2O}∞(en=ethylenediamine) with cube-like W8Cu12 units from a coordinated anion template self-assembly reaction. New J Chem, 2002, 26(4): 485–486
Gillon B, Goujon A, Willemin S, Larionova J, Desplanches C, Ruiz E, André G, Stride J A, Guérin C. Neutron diffraction and theoretical DFT studies of two dimensional molecular-based magnet K2[Mn(H2O)2]3[Mo(CN)7]2·6H2O. Inorg Chem, 2007, 46(4): 1090–1099
Korzeniak T, Stadnicka K, Rams M, Sieklucka B. Grid-type two- di-mensional magnetic multinuclear metal complex: Strands of {[CuII(μ-4,4′-bpy)]2+{n cross-linked by octacyanotungstate (V) Ions. Inorg Chem, 2004, 43(16): 811–4813
Ma B Q, Sun H L, Gao S, Xu G X. Variable dimensionality from mononuclear and trinuclear to one and two dimensions: A series of copper (II) compounds with 4,4′-dipyridine dioxide. Inorg Chem, 2001, 40(24): 6247–6253
Simpon P G, Vinciguerra A, Quagliano J V. The donor properties of 2,2′-bipyridine N,N′-dioxide. Inorg Chem, 1963, 2(2): 282–286
Leipoldt J G, Bok L D C, Cilliers P J. The preparation of potassium octacyanotungstate (IV) dehydrate. Z Anorg Allg Chem, 1974, 407(3): 350–352
Bok L D C, Leipoldt J G, Basson S S. The preparation of Cs3Mo (CN)8·2H2O and Cs3W(CN)8·2H2O. Z Anorg Allg Chem, 1975, 415(1): 81–83
Sheldrick G M. SHELXL 97, program for crystal structure refinement. Germany: University of Göttingen, 1998
Ni Z H, Kou H Z, Zheng L, Zhao Y H, Zhang L F, Wang R J, Cui A L, Sato O. Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: Syntheses, crystal struc-tures, and magnetic properties. Inorg Chem, 2005, 44(13): 4728–4736