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A novel 2D inorganic–organic hybrid compound constructed from {CuMo2O7}n bimetallic oxide chains bridged by N-containing ligand
A novel 2D inorganic-organic hybrid compound constructed from{CuMo 2 O7}n bimetallic oxide chains bridged by N-containing ligand Xiang-Guang Guo, Wen-Bin Yang, Xiao-Yuan Wu, Qi-Kai Zhang, Lang Lin, Can-Zhong Lu PII: DOI: Reference:
S1387-7003(14)00204-4 doi: 10.1016/j.inoche.2014.04.033 INOCHE 5572
To appear in:
Inorganic Chemistry Communications
Received date: Revised date: Accepted date:
21 March 2014 21 April 2014 25 April 2014
Please cite this article as: Xiang-Guang Guo, Wen-Bin Yang, Xiao-Yuan Wu, Qi-Kai Zhang, Lang Lin, Can-Zhong Lu, A novel 2D inorganic-organic hybrid compound constructed from{CuMo2 O7 }n bimetallic oxide chains bridged by N-containing ligand, Inorganic Chemistry Communications (2014), doi: 10.1016/j.inoche.2014.04.033
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT A novel 2D inorganic-organic hybrid compound constructed
N-containing ligand
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from {CuMo2O7}n bimetallic oxide chains bridged by
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Xiang-Guang Guoa,b, Wen-Bin Yanga,b, Xiao-Yuan Wua,b, Qi-Kai Zhanga,b, Lang Lina,b, Can-Zhong Lua,b*
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a. Key Laboratory of Design and Assembly of Functional Nanostructures, Chinese Academy of
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Sciences; b. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China; *Corresponding author: Fax: +86-591-83714946. Telephone: +86-591-83705794. E-mail:
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[email protected].
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Abstract: A novel inorganic-organic hybrid compound [Cu(Mo2O7)(H2MDP)] (1) has been hydrothermally synthesized from the self-assembly of CuI, H2MoO4 and
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H2MDP ([Methylenebis(3,5-dimethylpyrazole)]). Compound 1 is constructed from
AC
one-dimensional {Cu(Mo2O7)}n bimetallic oxide chains bridged by H2MDP ligands into a novel two-dimensional hybrid compound. There exist left- and right-handed Cu-O-Mo helical chains in the bimetallic oxide chains. Key words: hybrid compound; hydrothermal synthesis; bimetallic oxide chain, helical chains
The exploration of molybdenum oxide based inorganic-organic hybrid materials is of great interest not only due to their fascinating architectures but also because of their potential applications in magnetic, optical fields and so on.[1-4] One attractive 1
ACCEPTED MANUSCRIPT approach for the preparation of new metal oxide hybrid materials is to exploit organic molecules to modify inorganic microstructures.[5-6] Zubieta and co-workers have
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introduced secondary metal-ligand coordination complex cations synthetic strategy to
CR
prepare various molybdenum oxides, which has been successfully used in the development of the chemistry of bimetallic oxides of the copper molybdate family
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Cu/Mo/O/ligand.[7-9] Some bidentate chelating organoamine ligands such as
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o-Phenanthroline, 2, 2’-bipyridine, 2, 3-bis(2-pyridyl)pyrazine have been used in the preparation of such hybrid materials. In this article, we choose the flexible H2MDP ([Methylenebis(3,5-dimethylpyrazole)]) ligand which has proven to be a good ditopic
ED
ligand in the construction of coordination polymers with diverse structures.[10-11]
PT
However, it is never involved in the self-assembly of polyoxometalate-based materials. Herein by introducing the H2MDP ligand we report the synthesis and characterization a
novel
two-dimensional
CE
of
bimetallic
inorganic-organic
framework,
chains.
AC
[Cu(H2MDP)(Mo2O7)] (1), which contains left- and right-handed Cu-O-Mo helical
Green crystals of 1 were hydrothermally synthesized by mixing CuI, H2MoO4 and H2MDP in distilled water at 180 °C for 3 days.[12] The structure of 1 was characterized by single-crystal X-ray diffraction, element analysis, IR.[13] The pure phase was confirmed by PXRD (Fig. S1).The asymmetric unit contains one Cu(H2MDP)2+ ion and one Mo2O72- anion. As shown in Fig. 1b, one dinuclear molybdenum oxide unit was assembled from two edge-sharing [Mo1O5] square pyramids with Mo-O bond lengths from 1.700(11) to 2.125(9) Å, while another 2
ACCEPTED MANUSCRIPT dinuclear molybdenum oxide unit from two edge-sharing [Mo2O6] distorted octahedra with Mo-O bond lengths from 1.663(10) to 2.504(10) Å (Fig. 1b). Each Cu
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center is coordinated by four oxygen atoms from three Mo2O72- anions and two
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nitrogen atoms from two H2MDP ligand, showing a distorted octahedral [CuN2O4] coordination geometry. The basal plane of the Cu octahedron is defined by two
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nitrogen atoms from two H2MDP ligands and two oxygen atoms from molybdate
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cluster (Cu1-N2 = 1.979(12) Å, Cu1-N4 = 1.986(12) Å, Cu1-O5 = 2.052 Å, Cu1-O2 = 1.994(10) Å), while the apical position is occupied by two oxygen atoms with longer Cu-O bond lengths (Cu1-O3 = 2.319(11), Cu1-O6 = 2.331(10) Å). The
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significantly longer Cu-O bond lengths in the apical position is caused by the
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CE
polymers.[14]
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Jahn-Teller effect, which are comparable to those previously reported Cu
Figure 1. (a) View of the coordination environment of metal atoms (all hydrogen atoms are omitted for clarity); (b) View of molybdenum oxide cluster; (c) Representation of connection between structural unit [MoOx] and [CuN2O4]; (d) View of 1D bimetallic oxide chains {Cu(Mo2O7)}n; (e) View of 2D hybrid framework constructed from bimetallic oxide chains bridged by H2MDP ligands. 3
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ACCEPTED MANUSCRIPT
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Scheme 1. Representation of coordination between Cu(II) centers 1.
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The two-dimensional layer structure of 1 is constructed from copper-molybdenum bimetallic {Cu(Mo2O7)}n chains and tethered (H2MDP)n ligands occupying the
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interchain region (Fig. 1d, e). The identical bimetallic {Cu(Mo2O7)}n chains have been reported by Zubieta and co-workers in three compounds: [Cu(2,2’-bpy)Mo2O7],
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[Cu(pyrpyrz)Mo2O7], [Cu(tpa)Mo2O7].[15-17] However, the above compounds are all
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one-dimensional chains structure due to bidentate N-containing chelating ligands used, which block the formation high-dimensional networks. As reported previously, the
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H2MDP ligand has the tendency to form a M2L2-type metallocyclic motif. Furthermore each M2L2 motif can connect two molybdenum oxide chains to form high-dimensional networks. In the bimetallic oxide chain, pairs of different dinuclear molybdenum oxide units assemble together to form a tetranuclear molybdenum oxide cluster extended to an infinite molybdenum oxide chain [Mo2O7]n2n- (Fig. 1b). Each [CuN2O4] octahedra is connected to one [Mo1O5] square-pyramid and one pair of [Mo2O6] octahedra through corner- and edge-sharing, respectively (Fig. 1c). It is noted that there are closed loops constructed from two H2MDP ligands and two copper atoms, in which the Cu…Cu distance is 8.4527(19) Å (Fig. 1e). 4
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Figure 2. (a) A view of the left-handed and right-handed Cu-O-Mo helical chains in 1;
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(b) Polyhedral view of two kinds of helical chains; (c) Representation of connections between pairs of [Mo2O6] octahedra and helical chains. Compound
1
consists
of
helical
chains
constructed
from
[Mo1O5]
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square-pyramids and [CuN2O4] octahedra. As shown in Fig. 2a, b, the [Mo1O5]
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square-pyramids and [CuN2O4] octahedra are corner-shared to form left- and right-handed helical chains. The space between two helical chains is occupied by pairs
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of [Mo2O6] octahedra through edge-sharing (Fig. 2c).
Figure 3.Plots of χmT and χm−1 versus T for complexes 1. The temperature dependence of the magnetic susceptibility of 1 in the 2–300 K temperature range under an applied field of 1000 Oe, as is shown in Fig. 3. The χmT value at room temperature is 0.440 cm3 mol-1 K, slightly higher than the spin-only value expected for one isolated Cu2+ center (0.375 cm3 mol-1 K and S = 1/2).[18-20] 5
ACCEPTED MANUSCRIPT In complex 1, the χmT value decreases to 0.128 cm3 K mol-1 at 13.8 K, then increases sharply to 0.18 cm3 mol-1 K at about 11.4 K, and then finally drops until the lowest
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temperature 2 K. The best fit with the Curie-Weiss law gives C = 0.468 cm3 mol-1 K
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and θ = -16.1 K, indicating weak antiferromagnetic interactions among the isolated magnetic Cu2+ ions, through the long pathway of Cu-O-Mo-O-Cu. The
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antiferromagnetic coupling dominates in a higher temperature region above 50 K,
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whereas the abrupt increase in χmT value below 13 K suggests the weak ferromagnetism, which is probably related to spin-canting.[21-22] In summary, under hydrothermal condition we have isolated a new
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inorganic-organic hybrid framework constructed from copper-molybdenum bimetallic
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oxide {Cu(Mo2O7)}n chains, which contains left- and right-handed Cu-O-Mo helical chains.
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Acknowledgements
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This work was supported by the Chinese Academy of Sciences (KJCX2-YW-319, KJCX2-EW-H01), the 973 key program of the MOST (2010CB933501, 2012CB821705), the National Natural Science Foundation of China and the Natural Science
Foundation
of
Fujian
Province
(2007HZ0001-1,
2009HZ0004-1,
2009HZ0005-1, 2009HZ0006-1, 2006L2005). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi: References 6
ACCEPTED MANUSCRIPT [1] Y. Q. Lan, S. L. Li, X. L. Wang, K. Z. Shao, D. Y. Du, H. Y. Zang, Z. M. Su, Self-assembly of polyoxometalate-based metal organic frameworks based on
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octamolybdates and copper-organic units: from Cu-II, Cu-I,Cu-II to Cu-I via
CR
changing organic amine, Inorg. Chem., 47 (2008) 8179-8187.
[2] Y. M. Xie, R. M. Yu, X. Y. Wu, F. Wang, J. Zhang, C. Z. Lu, Synthesis, structure,
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and magnetic properties of a novel polyoxometalate-organic framework with
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unusual (5,6)-connected topology, Cryst. Growth Des., 11 (2011) 4739-4741. [3] P. Dong, Q. K. Zhang, F. Wang, S. C. Chen, X. Y. Wu, Z. G. Zhao, C. Z. Lu, A new molybdenum-oxide-based organic-inorganic hybrid compound templated by
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5-(2-pyridyl)tetrazole with new topology and canted antiferromagnetism, Cryst.
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Growth Des., 10 (2010) 3218-3221. [4] X. Y. Wu, P. Dong, R. M. Yu, Q. K. Zhang, X. F. Kuang, S. C. Chen, Q. P. Lin, C.
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Z. Lu, A 2D polyoxometalate-based complex: spin-canting and metamagnetism,
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CrystEngComm, 13 (2011) 3686-3688. [5] P. J. Hagrman, D. Hagrman, J. Zubieta, Organic-inorganic hybrid materials: From “Simple” coordination polymers to organodiamine-templated molybdenum oxides, Angew. Chem. Int. Ed., 38 (1999) 2638-2684. [6] D. J. Chesnut, D. Hagrman, P. J. Zapf, R. P. Hammond, R. LaDuca Jr, R. C. Haushalter, J. Zubieta, Organic/inorganic composite materials: the roles of organoamine ligands in the design of inorganic solids, Coord. Chem. Rev., 190-192 (1999) 737-769.
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ACCEPTED MANUSCRIPT [7] D. Hagrman, R. C. Haushalter, J. Zubieta, Three-dimensional organic/inorganic hybrid materials constructed from one-dimensional copper diamine coordination
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polymers linked by bridging oxoanion tetrahedra: [Cu(dpe)(MoO4)] and
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[Cu(dpe)(SO4)(H2O)] (dpe = 1,2-trans-(4-pyridyl)ethene), Chem. Mater., 10 (1998) 361-365.
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[8] D. Hagrman, C. J. Warren, R. C. Haushalter, C. Seip, C. J. O'Connor, R. S. Rarig,
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K. M. Johnson, R. L. LaDuca, J. Zubieta, Structure-directing role of organoamine ligands in the self-assembly of novel bimetallic oxides, Chem. Mater., 10 (1998) 3294-3297.
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[9] D. Hagrman, P. J. Hagrman, J. Zubieta, Solid-State Coordination Chemistry: The
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self-assembly of microporous organic-inorganic hybrid frameworks constructed from tetrapyridylporphyrin and bimetallic oxide chains or oxide clusters, Angew.
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Chem. Int. Ed., 38 (1999) 3165-3168.
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[10] T. Basu, H. A. Sparkes, M. K. Bhunia, R. Mondal, Identification of reaction conditions that can reproducibly lead to a particular vertex geometry: Quest for a robust and reproducible metal-carboxylate Noncluster-type SBU, Cryst. Growth Des., 9 (2009) 3488-3496. [11] X. G. Guo, W. B. Yang, X. Y. Wu, Q. K. Zhang, L. Lin, R. M. Yu and C. Z. Lu, Stoichiometry, temperature, solvent, metal-directed syntheses of metal–organic frameworks based on flexible V-shaped methylenebis(3,5-dimethylpyrazole) and various aromatic dicarboxylate acids, CrystEngComm, 15 (2013), 3654-3663.
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ACCEPTED MANUSCRIPT [12] Synthesis of 1: A mixture of H2MoO4 (0.1 g, 0.62 mmol), CuI (0.1 g, 0.52 mmol), H2MDP (0.040 g, 0.2 mmol), H2O (10 mL) was heated in a 23 mL Teflon-lined
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reaction vessel at 180 °C for 3 days. Then the autoclave was cooled at 3 °C h -1 to
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room temperature. The green block crystals were isolated, washed with water and dried at room temperature. Yield: (58% based on Mo). Elemental analysis
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(%) calcd for C11H16CuMo2N4O7: H, 2.80; C, 23.08; N, 9.79. Found: H, 2.96; C,
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22.70; N, 9.54. IR spectrum (KBr pellets, ν/cm-1): 3412 (m), 3259 (m), 1580 (w), 1464 (w), 1278 (w), 1185 (m), 949 (m), 920 (m), 890 (m), 837 (m), 760 (m), 620 (m).
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[13] Crystal data: C11H16CuMo2N4O7, M = 571.70, monoclinic, P2/c, a =11.7088(6),
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b = 7.1445(3), c = 20.8780(12) Å, α = 90, β = 105.433(6), γ = 90°, V = 1688.93(12) Å3, Z = 4, T =293(2) K, 6188 reflections measured, 3323
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independent reflections (Rint = 0.0347). The final R1 value was 0.0675 (I > 2σ(I)).
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The final wR(F2) value was 0.2518 (I > 2σ(I)). The final R1 value was 0.0766 (all data). The final wR(F2) value was 0.2584 (all data). The crystallographic calculations were conducted using the SHELXL-97 programs. [14] H. Q. Hao, W. T. Liu, W. Tan, Z. J. L, M. L. Tong, Spontaneous resolution of chiral metal mandelates by stereochemical control, CrystEngComm, 11 (2009), 967-971. [15] P. J. Zapf, C. J. Warren, R. C. Haushalter, J. Zubieta, One- and two-dimensional organic-inorganic composite solids constructed from molybdenum oxide clusters
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ACCEPTED MANUSCRIPT and chains linked through {M(2,2’-bpy)}2+ fragments (M = Co, Ni, Cu), Chem. Commun., (1997) 1543-1544.
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[16] R. S. Rarig Jr, P. J. Hagrman, J. Zubieta, Ligand influences on the structures of
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copper molybdate chains: hydrothermal synthesis and structural characterizations of [Cu(2,2’-bipyridine)Mo4O13] and [Cu(2,3-bis(2-pyridyl)pyrazine)Mo2O7], Solid
US
State Sci., 4 (2002) 77-82.
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[17] R.S. Rarig, C. Bewley, E. Burkholder, J. Zubieta, Organic-inorganic hybrid materials of the copper molybdate family. syntheses and structures of [Cu(tpa)Mo2O7],
[Cu(Me2bpy)Mo2O7] Me2bpy
=
Mo4O13]
(tpa
5,5’-dimethyl-2,2’-bipyridine, t-Bu2bpy
= =
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tri-2-pyridylamine,
and [Cu(t-Bu2bpy)
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4,4’-di-tert-butyl-2,2'-bipyridine), Indian J. Chem., 42A (2003) 2235. [18] M. Zhu, S. Q. Su, X. Z. Song, Z. M. Hao, S. Y. Song, H. J. Zhang, Spin canting
CE
magnetization in a 3D Cu(ii) complex based on molybdate oxide cluster and
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5-triazole isophthalic acid, Dalton Trans., 41 (2012) 13267-13270. [19] X. Y. Song, Li, D. Z. Liao, Z. H. Jiang, S. P. Yan, Extended Tapes of Cyclic Water Hexamers in an unusual oxalate-bridged one-dimensional copper(II) complex, Cryst. Growth Des., 7 (2007) 1220-1222. [20] J. Yang, S. W. Yan, X. Wang, D. R. Xiao, H. Y. Zhang, X. L. Chi, J. L. Zhang, E.-B. Wang, An unusual polythreaded coordination network self-assembled from 2D motifs with two distinct lateral arms, Inorg. Chem. Comm., 38 (2013) 100-103.
10
ACCEPTED MANUSCRIPT [21] H. H. Chen, J. Yang, Y. Y. Liu, J. F. Ma, A series of tetranuclear-cluster containing complexes based on pendent-arm macrocyclic ligand and different
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carboxylates: syntheses, structures, photoluminescence, and magnetic properties,
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CrystEngComm, 15 (2013), 5168-5178.
[22] F. L. Liu, L. L. Zhang, R. M. Wang, J. Sun, J. Yang, Z. Chen, X. P. Wang, D. F.
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Sun, Five MOFs with different topologies based on anthracene functionalized
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tetracarboxylic acid: syntheses, structures, and properties, CrystEngComm, 16
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CE
PT
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(2014), 2917-2928.
11
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ACCEPTED MANUSCRIPT
Graphical Abstract
Here we present a novel 2D inorganic-organic hybrid compound constructed from
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{CuMo2O7}n bimetallic oxide chains, which contains left- and right-handed Cu-O-Mo
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CE
PT
helical chains.
12
ACCEPTED MANUSCRIPT
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Highlights
A new inorganic-organic hybrid compound with {Cu(Mo2O7)}n bimetallic oxide
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chains
An unprecedented hybrid materials tuned by [Methylenebis(3,5-dimethylpyrazole)]
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CE
PT
ED
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The compound consists of left- and right-handed helical chains
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S1387-7003(14)00204-4 doi: 10.1016/j.inoche.2014.04.033 INOCHE 5572
To appear in:
Inorganic Chemistry Communications
Received date: Revised date: Accepted date:
21 March 2014 21 April 2014 25 April 2014
Please cite this article as: Xiang-Guang Guo, Wen-Bin Yang, Xiao-Yuan Wu, Qi-Kai Zhang, Lang Lin, Can-Zhong Lu, A novel 2D inorganic-organic hybrid compound constructed from{CuMo2 O7 }n bimetallic oxide chains bridged by N-containing ligand, Inorganic Chemistry Communications (2014), doi: 10.1016/j.inoche.2014.04.033
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT A novel 2D inorganic-organic hybrid compound constructed
N-containing ligand
IP T
from {CuMo2O7}n bimetallic oxide chains bridged by
CR
Xiang-Guang Guoa,b, Wen-Bin Yanga,b, Xiao-Yuan Wua,b, Qi-Kai Zhanga,b, Lang Lina,b, Can-Zhong Lua,b*
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a. Key Laboratory of Design and Assembly of Functional Nanostructures, Chinese Academy of
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Sciences; b. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China; *Corresponding author: Fax: +86-591-83714946. Telephone: +86-591-83705794. E-mail:
ED
[email protected].
PT
Abstract: A novel inorganic-organic hybrid compound [Cu(Mo2O7)(H2MDP)] (1) has been hydrothermally synthesized from the self-assembly of CuI, H2MoO4 and
CE
H2MDP ([Methylenebis(3,5-dimethylpyrazole)]). Compound 1 is constructed from
AC
one-dimensional {Cu(Mo2O7)}n bimetallic oxide chains bridged by H2MDP ligands into a novel two-dimensional hybrid compound. There exist left- and right-handed Cu-O-Mo helical chains in the bimetallic oxide chains. Key words: hybrid compound; hydrothermal synthesis; bimetallic oxide chain, helical chains
The exploration of molybdenum oxide based inorganic-organic hybrid materials is of great interest not only due to their fascinating architectures but also because of their potential applications in magnetic, optical fields and so on.[1-4] One attractive 1
ACCEPTED MANUSCRIPT approach for the preparation of new metal oxide hybrid materials is to exploit organic molecules to modify inorganic microstructures.[5-6] Zubieta and co-workers have
IP T
introduced secondary metal-ligand coordination complex cations synthetic strategy to
CR
prepare various molybdenum oxides, which has been successfully used in the development of the chemistry of bimetallic oxides of the copper molybdate family
US
Cu/Mo/O/ligand.[7-9] Some bidentate chelating organoamine ligands such as
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o-Phenanthroline, 2, 2’-bipyridine, 2, 3-bis(2-pyridyl)pyrazine have been used in the preparation of such hybrid materials. In this article, we choose the flexible H2MDP ([Methylenebis(3,5-dimethylpyrazole)]) ligand which has proven to be a good ditopic
ED
ligand in the construction of coordination polymers with diverse structures.[10-11]
PT
However, it is never involved in the self-assembly of polyoxometalate-based materials. Herein by introducing the H2MDP ligand we report the synthesis and characterization a
novel
two-dimensional
CE
of
bimetallic
inorganic-organic
framework,
chains.
AC
[Cu(H2MDP)(Mo2O7)] (1), which contains left- and right-handed Cu-O-Mo helical
Green crystals of 1 were hydrothermally synthesized by mixing CuI, H2MoO4 and H2MDP in distilled water at 180 °C for 3 days.[12] The structure of 1 was characterized by single-crystal X-ray diffraction, element analysis, IR.[13] The pure phase was confirmed by PXRD (Fig. S1).The asymmetric unit contains one Cu(H2MDP)2+ ion and one Mo2O72- anion. As shown in Fig. 1b, one dinuclear molybdenum oxide unit was assembled from two edge-sharing [Mo1O5] square pyramids with Mo-O bond lengths from 1.700(11) to 2.125(9) Å, while another 2
ACCEPTED MANUSCRIPT dinuclear molybdenum oxide unit from two edge-sharing [Mo2O6] distorted octahedra with Mo-O bond lengths from 1.663(10) to 2.504(10) Å (Fig. 1b). Each Cu
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center is coordinated by four oxygen atoms from three Mo2O72- anions and two
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nitrogen atoms from two H2MDP ligand, showing a distorted octahedral [CuN2O4] coordination geometry. The basal plane of the Cu octahedron is defined by two
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nitrogen atoms from two H2MDP ligands and two oxygen atoms from molybdate
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cluster (Cu1-N2 = 1.979(12) Å, Cu1-N4 = 1.986(12) Å, Cu1-O5 = 2.052 Å, Cu1-O2 = 1.994(10) Å), while the apical position is occupied by two oxygen atoms with longer Cu-O bond lengths (Cu1-O3 = 2.319(11), Cu1-O6 = 2.331(10) Å). The
ED
significantly longer Cu-O bond lengths in the apical position is caused by the
AC
CE
polymers.[14]
PT
Jahn-Teller effect, which are comparable to those previously reported Cu
Figure 1. (a) View of the coordination environment of metal atoms (all hydrogen atoms are omitted for clarity); (b) View of molybdenum oxide cluster; (c) Representation of connection between structural unit [MoOx] and [CuN2O4]; (d) View of 1D bimetallic oxide chains {Cu(Mo2O7)}n; (e) View of 2D hybrid framework constructed from bimetallic oxide chains bridged by H2MDP ligands. 3
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ACCEPTED MANUSCRIPT
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Scheme 1. Representation of coordination between Cu(II) centers 1.
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The two-dimensional layer structure of 1 is constructed from copper-molybdenum bimetallic {Cu(Mo2O7)}n chains and tethered (H2MDP)n ligands occupying the
ED
interchain region (Fig. 1d, e). The identical bimetallic {Cu(Mo2O7)}n chains have been reported by Zubieta and co-workers in three compounds: [Cu(2,2’-bpy)Mo2O7],
PT
[Cu(pyrpyrz)Mo2O7], [Cu(tpa)Mo2O7].[15-17] However, the above compounds are all
CE
one-dimensional chains structure due to bidentate N-containing chelating ligands used, which block the formation high-dimensional networks. As reported previously, the
AC
H2MDP ligand has the tendency to form a M2L2-type metallocyclic motif. Furthermore each M2L2 motif can connect two molybdenum oxide chains to form high-dimensional networks. In the bimetallic oxide chain, pairs of different dinuclear molybdenum oxide units assemble together to form a tetranuclear molybdenum oxide cluster extended to an infinite molybdenum oxide chain [Mo2O7]n2n- (Fig. 1b). Each [CuN2O4] octahedra is connected to one [Mo1O5] square-pyramid and one pair of [Mo2O6] octahedra through corner- and edge-sharing, respectively (Fig. 1c). It is noted that there are closed loops constructed from two H2MDP ligands and two copper atoms, in which the Cu…Cu distance is 8.4527(19) Å (Fig. 1e). 4
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ACCEPTED MANUSCRIPT
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Figure 2. (a) A view of the left-handed and right-handed Cu-O-Mo helical chains in 1;
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(b) Polyhedral view of two kinds of helical chains; (c) Representation of connections between pairs of [Mo2O6] octahedra and helical chains. Compound
1
consists
of
helical
chains
constructed
from
[Mo1O5]
ED
square-pyramids and [CuN2O4] octahedra. As shown in Fig. 2a, b, the [Mo1O5]
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square-pyramids and [CuN2O4] octahedra are corner-shared to form left- and right-handed helical chains. The space between two helical chains is occupied by pairs
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CE
of [Mo2O6] octahedra through edge-sharing (Fig. 2c).
Figure 3.Plots of χmT and χm−1 versus T for complexes 1. The temperature dependence of the magnetic susceptibility of 1 in the 2–300 K temperature range under an applied field of 1000 Oe, as is shown in Fig. 3. The χmT value at room temperature is 0.440 cm3 mol-1 K, slightly higher than the spin-only value expected for one isolated Cu2+ center (0.375 cm3 mol-1 K and S = 1/2).[18-20] 5
ACCEPTED MANUSCRIPT In complex 1, the χmT value decreases to 0.128 cm3 K mol-1 at 13.8 K, then increases sharply to 0.18 cm3 mol-1 K at about 11.4 K, and then finally drops until the lowest
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temperature 2 K. The best fit with the Curie-Weiss law gives C = 0.468 cm3 mol-1 K
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and θ = -16.1 K, indicating weak antiferromagnetic interactions among the isolated magnetic Cu2+ ions, through the long pathway of Cu-O-Mo-O-Cu. The
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antiferromagnetic coupling dominates in a higher temperature region above 50 K,
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whereas the abrupt increase in χmT value below 13 K suggests the weak ferromagnetism, which is probably related to spin-canting.[21-22] In summary, under hydrothermal condition we have isolated a new
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inorganic-organic hybrid framework constructed from copper-molybdenum bimetallic
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oxide {Cu(Mo2O7)}n chains, which contains left- and right-handed Cu-O-Mo helical chains.
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Acknowledgements
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This work was supported by the Chinese Academy of Sciences (KJCX2-YW-319, KJCX2-EW-H01), the 973 key program of the MOST (2010CB933501, 2012CB821705), the National Natural Science Foundation of China and the Natural Science
Foundation
of
Fujian
Province
(2007HZ0001-1,
2009HZ0004-1,
2009HZ0005-1, 2009HZ0006-1, 2006L2005). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi: References 6
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ACCEPTED MANUSCRIPT [12] Synthesis of 1: A mixture of H2MoO4 (0.1 g, 0.62 mmol), CuI (0.1 g, 0.52 mmol), H2MDP (0.040 g, 0.2 mmol), H2O (10 mL) was heated in a 23 mL Teflon-lined
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reaction vessel at 180 °C for 3 days. Then the autoclave was cooled at 3 °C h -1 to
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room temperature. The green block crystals were isolated, washed with water and dried at room temperature. Yield: (58% based on Mo). Elemental analysis
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(%) calcd for C11H16CuMo2N4O7: H, 2.80; C, 23.08; N, 9.79. Found: H, 2.96; C,
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22.70; N, 9.54. IR spectrum (KBr pellets, ν/cm-1): 3412 (m), 3259 (m), 1580 (w), 1464 (w), 1278 (w), 1185 (m), 949 (m), 920 (m), 890 (m), 837 (m), 760 (m), 620 (m).
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[13] Crystal data: C11H16CuMo2N4O7, M = 571.70, monoclinic, P2/c, a =11.7088(6),
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b = 7.1445(3), c = 20.8780(12) Å, α = 90, β = 105.433(6), γ = 90°, V = 1688.93(12) Å3, Z = 4, T =293(2) K, 6188 reflections measured, 3323
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independent reflections (Rint = 0.0347). The final R1 value was 0.0675 (I > 2σ(I)).
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The final wR(F2) value was 0.2518 (I > 2σ(I)). The final R1 value was 0.0766 (all data). The final wR(F2) value was 0.2584 (all data). The crystallographic calculations were conducted using the SHELXL-97 programs. [14] H. Q. Hao, W. T. Liu, W. Tan, Z. J. L, M. L. Tong, Spontaneous resolution of chiral metal mandelates by stereochemical control, CrystEngComm, 11 (2009), 967-971. [15] P. J. Zapf, C. J. Warren, R. C. Haushalter, J. Zubieta, One- and two-dimensional organic-inorganic composite solids constructed from molybdenum oxide clusters
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[Cu(Me2bpy)Mo2O7] Me2bpy
=
Mo4O13]
(tpa
5,5’-dimethyl-2,2’-bipyridine, t-Bu2bpy
= =
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tri-2-pyridylamine,
and [Cu(t-Bu2bpy)
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4,4’-di-tert-butyl-2,2'-bipyridine), Indian J. Chem., 42A (2003) 2235. [18] M. Zhu, S. Q. Su, X. Z. Song, Z. M. Hao, S. Y. Song, H. J. Zhang, Spin canting
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Sun, Five MOFs with different topologies based on anthracene functionalized
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tetracarboxylic acid: syntheses, structures, and properties, CrystEngComm, 16
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(2014), 2917-2928.
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Graphical Abstract
Here we present a novel 2D inorganic-organic hybrid compound constructed from
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{CuMo2O7}n bimetallic oxide chains, which contains left- and right-handed Cu-O-Mo
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helical chains.
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ACCEPTED MANUSCRIPT
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Highlights
A new inorganic-organic hybrid compound with {Cu(Mo2O7)}n bimetallic oxide
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chains
An unprecedented hybrid materials tuned by [Methylenebis(3,5-dimethylpyrazole)]
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The compound consists of left- and right-handed helical chains
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