A novel 2-D structure constructed from copper complexes and bi-capped tungsten-based Keggin clusters

    A novel 2-D structure constructed from copper complexes and bi-capped tungsten-based Keggin clusters Ya-Bing Liu, Li-Wei Fu, Wei-Jie Duan, Li-Na Xiao, Yang-Yang Hu, De-Chuan Zhao, Hai-Yang Guo, Xiao-Bing Cui, Ji-Qing Xu PII: DOI: Reference:

S1387-7003(14)00219-6 doi: 10.1016/j.inoche.2014.05.010 INOCHE 5587

To appear in:

Inorganic Chemistry Communications

Received date: Revised date: Accepted date:

31 March 2014 13 May 2014 15 May 2014

Please cite this article as: Ya-Bing Liu, Li-Wei Fu, Wei-Jie Duan, Li-Na Xiao, Yang-Yang Hu, De-Chuan Zhao, Hai-Yang Guo, Xiao-Bing Cui, Ji-Qing Xu, A novel 2-D structure constructed from copper complexes and bi-capped tungsten-based Keggin clusters, Inorganic Chemistry Communications (2014), doi: 10.1016/j.inoche.2014.05.010

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

IP T

A novel 2-D structure constructed from copper complexes and bi-capped tungsten-based Keggin clusters

SC R

Ya-Bing Liu,a,b Li-Wei Fu,a Wei-Jie Duan,a Li-Na Xiao,a Yang-Yang Hu,a De-Chuan Zhao,a Hai-Yang Guo,a Xiao-Bing Cui,a* Ji-Qing Xu,a a

Department of Chemistry, Collage of Chemistry and State Key Laboratory of Inorganic Synthesis

Department of Materials Science and Engineering, Jilin Jianzhu University, Changchun, 130118,

MA

b

NU

and Preparative Chemistry. Jilin University, Changchun 130023, China

AC C

EP

TE

D

China

Corresponding author: Xiao-Bing Cui, E-mail: [email protected], tel: 86-431-88499132.

1

ACCEPTED MANUSCRIPT Abstract: A new compound, [Cu(en)2(H2O)]{[Cu0.5(en)]3[VVW6.5VIW3VV4.5IVO42Cu(en)2]}·3.5H2O

IP T

(1) (en = ethylenediamine), has been hydrothermally synthesized and characterized by elemental

SC R

analysis, IR, ESR, XPS, TG analysis and single-crystal X-ray diffraction analysis. Compound 1 exhibits a novel 2-D structure linked by 1-D infinite left- and right-handed helical chains and

NU

transition metal coordination fragments. Adjacent layers are further interconnected into a 3-D supramolecular structure via hydrogen bonds. The magnetic susceptibility of compound 1

MA

demonstrated the presence of antiferromagnetic interactions.

D

Hydrothermal synthesis; Keggin polyoxometalate; Transition metal complex; Magnetic

AC C

EP

TE

susceptibility.

2

ACCEPTED MANUSCRIPT Polyoxometalates (POMs), as a class of metal oxide clusters with abundant topologies, have

IP T

attracted considerable attention because of their applications in catalysis, sorption, electrical conductivity, magnetism and photochemistry [1]. Recently, a hot topic of POM chemistry is to find

SC R

some suitable POM species as building blocks that can be further connected by transition metal complexes (TMCs) into one-, two- and three-dimensional extended solid frameworks [2-16]. The

NU

diversity of POMs and TMCs has led to a wide array of extended hybrid materials. Keggin polyoxometalates and Keggin polyoxometalate derivatives have emerged as a major

MA

research focus due to their stability and diverse electronic, non-linear optical and anti-HIV active properties [1]. Keggin polyoxometalate derivatives can be mainly divided into two groups. Firstly,

D

one or more metal atoms of a Keggin anion (Mo, W, V, Nb and Ta) can be substituted by one or more

TE

secondary metal atoms, forming metal substituted Keggin polyanions [17]. Secondly, pits of a Keggin anion can be capped by M (M = Mo, V, Sb, As, Ni, Cu and Zn eta.), forming capped Keggin

EP

POMs. A large number of hybrid compounds with fascinating structure and desirable properties

AC C

constructed from capped Keggin POMs and transition metal complexes (TMCs) have been obtained [18-33]. As we all known, the study of capped Keggin POMs is mainly focused on molybdenum-based Keggin species. However, tungsten-based Keggin species have remained relatively unexplored owing to the kinetic sluggishness of tungstates relative to molybdates. There are almost no reports on 1-D, 2-D or 3-D coordination structures constructed from bi-capped tungsten-based

Keggin

anions

and

TMCs.

Here,

we

present

a

compound,

[Cu(en)2(H2O)]{[Cu0.5(en)]3[VVW6.5VIW3VV4.5IVO42Cu(en)2]}·3.5H2O (1) (en = ethylendiamine), which shows a novel 2-D layer structure constructed from TMCs and bi-capped tungsten-based Keggin anions. Compound 1 was prepared by the conventional hydrothermal method [34]. Compound 1 was obtained from the reaction of Na2WO4·2H2O, V2O5, CuSO4·5H2O, H2C2O4·2H2O, en (ethylendiamines) and H2O [35]. The crystal analysis [36] reveals that compound 1 is formed by [VVW6.5VIW3VV4.5IVO42]7-,

[Cu(en)2]2+,

[Cu(en)2(H2O)]2+,

and

lattice

water

molecules. 3

ACCEPTED MANUSCRIPT [VVW6.5VIW3VV4.5IVO42]7-, as shown in Fig.1 and Fig. s1, has a bi-capped Keggin structure, which

IP T

can be regarded as a Keggin core with two V=O units capping its two opposite pits. There are eight

SC R

tungstens in the bi-capped Keggin anion, each of which exhibits a WO6 octahedral geometry with W-Ot (terminal oxygens) distances of 1.69(1)-1.73(1) Ǻ, W-Ob (bridging oxygens) distances of

NU

1.81(1)-2.06(9) Ǻ and W-Oc (central oxygens) distances of 2.35(1)-2.39(9) Ǻ . Except for the eight tungstens, the other four metal centers of the Keggin core of the bi-capped Keggin anion are

MA

disorderedly occupied by W and V with occupancy factors of 0.25, 0.75, 0.25, 0.75, 0.5, 0.5 and 0.5, 0.5, respectively. The four disorderedly occupied metal centers also exhibit an octahedral geometry

D

with M-Ot (terminal oxygens) distances of 1.65(1)-1.68(9) Ǻ, M-Ob (bridging oxygens) distances of

TE

1.89(9)-2.01(1) Ǻ and M-Oc (central oxygens) distances of 2.34(9)-2.41(1) Ǻ. The three vanadiums

EP

of the bi-capped Keggin anion display two different geometries, including a VO4 tetrahedron at the

AC C

center with V(1)-O bond lengths of 1.68(9)-1.70(9) Ǻ and two VO5 square pyramids at the two capping pits of the Keggin core with V-Ot distances of 1.61(1)-1.62(2) Ǻ and V-Ob distances of 1.90(1)-2.07(1) Ǻ.

Bond valence sums (BVS) [37] for the vanadiums fall within the range 4.03-4.16 except for V1. V(1) have a BVS value of 5.39 and therefore is presumed to be in the +5 oxidation state. The other vanadiums are in the +4 the oxidation state. Bond valence sums (BVS) calculations [37] for the tungstens give values of 5.61-6.05 which do not clearly identify the three reduced WV sites due to the delocalization of the d electrons of the reduced tungsten centers over the polyanion framework [38-42]. XPS spectra of 1 are shown in Fig.s2, and the XPS estimation seems to be in reasonable agreement with those calculated from bond valence sum calculations. The results further confirm the formula of the anion is [VVW6.5VIW3VV4.5IVO42]7-. 4

ACCEPTED MANUSCRIPT Here insert Fig.2

IP T

There are five crystallographic independent coppers in compound 1. As shown in Fig. 1, Cu(1) is coordinated by four nitrogens from two ethylendiamines and an oxygen from a neighboring POM. is

to

say,

the

copper

complex

[Cu(1)(en)2]2+

is

linked

SC R

That

to

a

neighboring

[VVW6.5VIW3VV4.5IVO42]7- through Cu(1)-O(11) contact with a bond distance of 2.59(1) Ǻ，forming a

NU

POM supported transition metal complex {[VVW6.5VIW3VV4.5IVO42][Cu(en)2]}5-. Both Cu(2) and Cu(3) are located at special positions and each of which receives contributions from four nitrogens

MA

belonging to two en. Cu(2) receives two extra contributions from two terminal oxygens belonging to two neighboring {[VVW6.5VIW3VV4.5IVO42][Cu(en)2]}5- with a Cu(2)-O(19) distance of 2.56(1) Ǻ,

D

whereas Cu(3) receives two extra contributions from two bridging oxygens belonging to two

TE

neighboring {[VVW6.5VIW3VV4.5IVO42][Cu(en)2]}5- with a Cu(3)-O(31) distance of 2.84(1) Ǻ. Thus,

EP

[Cu(2)(en)2]2+ and [Cu(3)(en)2]2+ interconnects two neighboring polyanions through Cu-O bonds to yield an unusual infinite helical chain. As shown in Fig. s3, detailed analysis reveals that the most

AC C

remarkable feature of 1 is that the 1-D helical chains can be divided into two different kinds, one is right-handed helical chain, and the other is a left-handed helical one. Cu(4) is also located at a special position and bonded to four nitrogens from two en and two oxygens from two neighboring POMs. It should be note that one of two neighboring POMs is from a right-handed helical chain, and the other of the two neighboring POMs is from a left-handed helical chain. [Cu(4)(en)2]2+ therefore joins two neighboring left- and right-handed 1-D helical chains into a 2-D waving framework structure along ab plane through Cu(4)-O(36) contact with a bond distance of 2.49(1) Ǻ (Fig. 2). [Cu(5)(en)2(H2O)]2+ only acts as a countercation in 1, which exhibits a square pyramidal geometry with four nitrogens from two en and an oxygen from a water molecules. The distance of Cu(5)-O(W1) is 2.64(1) Å. All Cu-N distances in compound 1 are in the range of 1.95(1)- 2.02(1) Å. As far as we know, it is the first 2-D framework constructed from bi-capped tungsten-based Keggin anions and TMCs. The ESR spectrum of compound 1 at room temperature shows a Cu (II) signal 5

ACCEPTED MANUSCRIPT

IP T

with g = 2.036, confirming the presence of Cu (II) (Fig. s4).

Hydrogen bonds play important roles in stabilizing the crystal structure of compound 1. As

SC R

shown in Fig. 3a, OW(2) (and its symmetry equivalents) links O(20) (and its symmetry equivalents) and O(7) (and its symmetry equivalents) from adjacent 2-D layer structures (Fig. 3b) with O∙∙∙O

NU

distances of 3.10(1) Å and 3.09(1) Å, respectively, generating a 3-D supramolecular network. The extended structure can be simplified into a 3-D topology as shown in Fig. 3c. Detailed analysis

MA

shows that there are hydrogen-bonding interactions between both carbons and nitrogens of en ligands and oxygens of polyoxoanions. These strong hydrogen bonding interactions in compound 1

D

are listed in Table s1. The TG curve of 1 is well consistent with the sum of the release of en ligands

TE

and water molecules of 1 (Calcd: 14.66%) (Fig. s5). The powder X-ray diffraction pattern for 1 is in agreement with the ones simulated based on the data of the single-crystal structure, indicating the

EP

purity of the as-synthesized products (Fig. s6). The differences in reflection intensity are probably

AC C

due to preferred orientations in the powder sample of compound 1.

The variable-temperature magnetic susceptibility of 1 was measured between 4 and 300 K at 5000Oe. The thermal variations of χm-1 and μeff of compound 1 are displayed in Fig. 4. The μeff continuously decreases as the temperature is lowered, indicating the presence of antiferromagnetic exchange interactions in 1. The room temperature value (μeff = 4.29 μB) is smaller than the expected value (μeff = 5.74 μB), indicating that antiferromagnetic interactions exist in 1. Unfortunately, it is not easy to fit the experimental magnetic data of this hetero-polymetallic spin system using a suitable theoretical model [43]. However, magnetic data for 1 is fitted to Curie-Weiss law in the range of 51 to 300 K. The Curie constant (c) is 2.37 emu·K·mol-1 and the Weiss temperature (θ) is -1.06 K, characteristic of an overall antiferromagnetic interactions. Acknowledgments This work was supported by the National Natural Foundation of China (No. 21003056), the 6

ACCEPTED MANUSCRIPT National Natural Foundation of Jilin Province (No.201215173).

IP T

References:

SC R

(b) M.E. Davis, Ordered porous materials for emerging applications, Nature 417 (2002) 813-821. (c) N. Mizuno, M. Misono, Heterogeneous catalysis, Chem. Rev. 98 (1998) 199-218.

NU

(d) M. Fujita, Y. J. Kwon, O. Sasaki, K. Yamaguchi, K. Ogura, Interpenetrating molecular ladders and bricks, J. Am. Chem. Soc. 117 (1995) 7287-7288.

MA

(e) Y. Ogasawara, S. Uchida, N. Mizuno, States of water in ionic crystals of [Cr3O(OOCH)6(H2O)3]+ macrocation and α-Keggin-type polyoxometalate, J. Phys. Chem. C

D

111 (2007) 8218-8227.

TE

(f) P.P. Zhao, Y. Leng, M.J. Zhang, J. Wang, Y.J. Wu, J. Huang, A polyoxometalate-based

EP

PdII-coordinated ionic solid catalyst for heterogeneous aerobic oxidation of benzene to biphenyl, Chem. Commun. 48 (2012) 5721-5723.

AC C

(g) J. Thiel, P.I. Molina, M.D. Symes, L. Cronin, Insights into the self-assembly mechanism of the modular polyoxometalate “Keggin-Net” family of framework materials and their electronic properties, Cryst. Growth Des. 12 (2012) 902-908. (h) A. Wutkowski, B.R. Srinivasan, A.R. Naik, C. Schütt, C. Näther, W. Bensc, Synthesis, structure, and photochemistry of an organic heptamolybdate-monomolybdate, Eur. J. Inorg. Chem. (2011) 2254-2263. (i) Q. Wu, W.L. Chen, D. Liu, C. Liang, Y.G. Li, S.W. Lin, E.B. Wang, New class of organic–inorganic hybrid aggregates based on polyoxometalates and metal-schiff-base, Dalton Trans. 40 (2011) 56-61. N. Jiang, F.Y. Li, L. Xu, Y.G. Li, J.M. Li, New assembly of transition metal complexes based on [GeW9O34]10- building blocks: syntheses, crystal structures and magnetic properties, Inorg. Chem. Commun. 13 (2010) 372-375.

7

ACCEPTED MANUSCRIPT S.T. Zheng, J. Zhang, X.X. Li, W.H. Fang, G.Y. Yang, Cubic polyoxometalate organic molecular

IP T

cage, J. Am. Chem. Soc. 132 (2010) 15102-15103.

X. Wang, J. Peng, M. G. Liu, D.D. Wang, C.L. Meng, Y. Li, Z.Y. Shi, Polyoxoanion-enveloped

SC R

Ag/ptz inorganic-organic hybrid system: from a single to a double template, CrystEngComm. 14 (2012) 3220-3226.

NU

J.X. Meng, Y. Lu, Y.G. Li, H. Fu, E.B. Wang, Controllable self-assembly of four new metal–organic frameworks based on different phosphomolybdate clusters by altering the molar

MA

ratio of H3PO4 and Na2MoO4, CrystEngComm. 13 (2011) 2479-2486 J. Zhou，S.T. Zheng, W.H. Fang, G.Y. Yang, A new 2-D network containing {As4V16O42(H2O)}

D

cluster units, Eur. J. Inorg. Chem. (2009) 5075-5078

TE

X.B. Cui, J.Q. Xu, H. Meng, S.T. Zheng, G.Y. Yang, A novel chainlike As-V-O polymer based

EP

on a transition metal complex and a dimeric polyoxoanion, Inorg. Chem. 43 (2004) 8005-8007 H. Guo, K. Yu, Z.H. Su, C.M. Wang, C.X. Wang, B.B. Zhou, A novel 2D organic-inorganic

AC C

hybrid based on [P2W18O62]6- polyoxoanion and Cu-bbi coordination polymers, Inorg. Chem. Commun. 27 (2013) 43-46

H. Wu, J. Yang, Y.Y. Liu, J.F. Ma, pH-controlled assembly of two unusual entangled motifs based on a tridentate ligand and octamolybdate clusters 1D+1D→3D poly-pseudorotaxane and 2D→2D→3D polycatenation, Cryst. Growth Des. 12 (2012) 2272-2276 Y.Y. Li, C.L. Leng, J.W. Zhao, S.D. Chen, P.T. Ma, L.J. Chen, A six-connected 3-D framework [enH2]2[Cu(en)2]3[H2W12O42]·6H2O constructed from paratungstate-based polyoxometalate units, Inorg. Chem. Commun. 25 (2012) 35-38 Y.P. Ren, X.J. Kong, L.S. Long, R.B. Huang, L.S. Zheng. Anion-dependent assembly of cyclic structure, Cryst. Growth Des. 6 (2006) 572-576. C.Z. Lu, C.D. Wu, H.H. Zhuang, J.S. Huang, Three polymeric frameworks constructed from discrete molybdenum oxide anions and 4,4’-bpy-bridged linear polymeric copper cations, Chem. Mater. 14(2002) 2649-2655 8

ACCEPTED MANUSCRIPT X.L. Wang, J. Li, A.X. Tian, D. Zhao, G.C. Liu, H.Y. Lin, Assembly of three NiII-bis(triazole)

IP T

complexes by exerting the linkage and template roles of Keggin anions, Cryst. Growth Des. 11 (2011) 3456-3462.

Liu, P.P. Zhang, J. Peng, H.X. Meng, X. Wang, M. Zhu, D.D. Wang, C.L. Meng, K.

SC R

[14] M.G.

Alimaje, Organic-inorganic hybrids constructed from mixed-valence multinuclear copper

[15] A.

NU

complexes and templated by keggin polyoxometalates, Cryst. Growth Des. 12(2012) 1273-1281. Iturrospe, B. Artetxe, S. Reinoso, L.S. Felices, P. Vitoria, L. Lezama, J.M. Cutiérrez-Zorrilla,

MA

Copper (II) complexes of tetradentate pyridyl supported on Keggin polyoxometalates: single-crystal to single-crystal transformations promoted by reversible dehydration processes,

Liu, J.L. Luo, D.Q. Zhang, N.L. Wang, Z.J. Chen, D.B. Zhu, Spin glass behaviour in a 1D

TE

[16] C.M.

D

Inorg. Chem. 52 (2013) 3084-3093.

mixed molybdenum-vanadium heteropolyoxmetalate-bridged coordination polymer, Eur. J.

Vaddypally, H. Swapna, K.D. Samar, The first one-dimensional heterpoly tungstovanadate

AC C

[17] S.

EP

Inorg. Chem. (2004) 4774-4779.

coordination polymer: [(VVO4)W8VIM4O36(VIVO)2]n- (M = 0.71VIV+0.29WVI, n = 4.68), Inorg. Chem. Commun. 3 (2002) 996-999. [18] Y.B.

Liu, Y. Wang, L.N. Xiao, Y.Y. Hu, L.M. Wang, D.C. Zhao, H.Y. Guo, X.B. Cui, C.L. Pan,

J.Q. Xu, A novel chain structure constructed from copper complexes and dimers based on bi-capped Keggin clusters, Inorg. Chem. Commun. 35 (2013) 204-207. [19] Y.

Ding, J.X. Meng, W.L. Chen, E.B. Wang, Controllable assembly of four new POM-based

supramolecula compounds by altering the POM secondary building units from pseudo-Keggin to classical Keggin, CrystengComm.13 (2011) 2687-2689. [20] C.M.

Liu, D.Q. Zhang, D.B. Zhu, One- and two-dimensional coordination polymers constructed

from bicapped Keggin mixed molybdenum-vanadium heteropolyoxoanions and polynuclear copper(I) clusters bridged by asymmetrical bipyridine (2,4’-bipy and 2,3’-bipy) ligands, Cryst. Growth Des. 6 (2006) 524-529. 9

ACCEPTED MANUSCRIPT

Duan, C.L. Pan, J.Q. Xu, X.B. Cui, F.T. Xie, T.G. Wang, Two- and three-dimensional

SC R

[22] L.M.

IP T

[21]

frameworks constructed from bicapped keggin clusters, Eur. J. Inorg. Chem. (2003) 2578-2581. Liu, J.N. Xu, Y.B. Liu, Y.K. Lu, J.F. Song, X. Zhang, X.B. Cui, J.Q. Xu, T.G. Wang,

NU

[23] J.

Hydrothermal synthesis and characterization of the first tri-capped mono-supporting

MA

pseudo-Keggin type tungsovanadophosphate: {PW9VV3IVO40(VIVO)3[Cu(en)2]}10-, J. Solid State Chem. 180 (2007) 3456-3462.

Yuan, Y.G. Li, E.B. Wang, C.C. Tian, L. Wang, C.W. Hu, N.H. Hu, H.Q. Jia, Modified

D

[24] M.

TE

Polyoxometalates: hydrothermal syntheses and crystal structure of three novel reduced and capped Keggin derivatives decorated by transition metal complexes, Inorg. Chem. 42 (2003)

Xu, H.G. Zhu, H. Cai, X.Z. You, [MoV2MoVI6VIV8O40(PO4)]5–: the first polyanion with a

AC C

[25] Y.

EP

3670-3676.

tetra-capped Keggin structure, Chem. Commun. (1999) 787-788. [26] C.M.

Liu,

D.Q.

Zhang,

M.

Xiong,

D.B.

Zhu,

A

novel

two-dimensional

mixed

molybdenum-vanadium poloxometalate with two types of cobalt(II) complex fragments as bridges, Chem. Commun. (2002) 1416-1417. [27] W.B.

Yang, C.Z. Lu, X.P. Zhang, H.H. Zhuang, Hydrothermal synthesis of the first

vanadomolybdenum polyoxoaction with

“metal-Bonded” spherical framework, Inorg. Chem.

41 (2002) 4621-4623. [28] J.Q.

Sha, J. Peng, H.S. Liu, J. Chen, A.X. Tian, P.P. Zhang, Asymmetrical polar modification of a

bivanadium-capped Keggin POM by multiple Cu-N coordination polymeric chains, Inorg. Chem. 46 (2007) 11183-11189. [29] X.

B. Cui, G. Y. Yang,

[{(H2O)Ni(enMe)2MoV4MoVI4VV8(VVO4)O40}2{Ni(enMe)2}

[Ni(enMe)2]4·8H2O: the first dimmer of polyoxometalates linked through coordination fragment, 10

ACCEPTED MANUSCRIPT Chem. Lett. (2002) 1238-1239. Shi, X.J. Gu, J. Peng, Y. Xu, E.B. Wang, From molecular double-ladders to an

IP T

[30] Z.Y.

unprecedented polycatenation: a parallel catenated 3D network containing bicapped Keggin

[31] J.Y.

SC R

polyoxometalate clusters, Eur. J. Inorg. Chem. (2006) 385-388.

Niu, G. Chen, J.W. Zhao, C.F. Yu, P.T. Ma, J.P. Wang, A novel ring-

shaped

Cryst. Growth Des. 10 (2010) 4689-4692.

Xiao, Y. Wang, Y. Chen, Y. Png, G.D. Li, X.B. Cui, S.Y. Shi, T.G. Wang, Z.M. Gao, J.Q.

MA

[32] L.N.

NU

phosphovanadomolybdate built by bicapped pesudo-keggin clusters and copper(II) complexes,

Xu, A novel polyoxometalate tri-supported mixed-valent transition metal coordination complex,

Liu, D.Q. Zhang, D.B. Zhu, Mixed molybdenum-vanadium polyoxoanion-bridged

TE

[33] C.M.

D

Inorg. Chem. Commun. 13 (2010) 1217-1220.

trimetallic nanocluster complexes: hydrothermal syntheses

and crystal structure of

EP

{MoVI6MoV2VIV8O40(PO4)[Co(phen)2(H2O)2]}[Co(phen)2(OH)2(H2O)4]1/2

and

AC C

{MoVI5MoV3VIV8O40(PO4)[Co(phen)(en)(H2O)2]}[Co(phen)3]·1.5H2O, Cryst. Growth Des. 3 (2003) 363-368. [34] S.H.

Feng, R.R. Xu, New materials in hydrothermal synthesis, Acc. Chem. Res. 34 (2001)

239-247. [35] A

mixture of Na2WO4·2H2O (1.32 g, 4 mmol ), V2O5 (0.36 g, 2 mmol ), CuSO4·5H2O (0.50 g, 2

mmol ), H2C2O4·2H2O (0.50 g, 4.0 mmol ) and H2O (28 mL, 1560 mmol ) in a molar ratio of 2: 1: 1: 2: 780 was neutralized to pH = 7 with ethylenediamine (0.40 mL, 6.0 mmol ) under continuous stirring and sealed in a 40 mL of Teflon-lined autoclave with 70% filling and heated at 180°C for 3 days. After cooled to room temperature, the crystalline product was filtered, washed with distilled water and dried at ambient temperature to give 0.68 g solids (yield 59.6 % based on W). Anal for C14H65Cu3.5W9.5N14O46.5V5.5, Calc (%): C, 4.91; H, 1.88; N, 5.73; Cu, 6.50; W, 51.03; V, 8.19. Found: C, 4.87; H, 1.91 ; N, 5.72 ; Cu, 6.53; W, 51.10; V, 8.17. IR

11

ACCEPTED MANUSCRIPT (cm-1) (Fig. s7) : 3444(m), 3317(w), 3238(w), 2959(w), 1583(s), 1450(w), 1389(w), 1270(w),

[36] Reflection

IP T

1176(w), 1103(w), 1044(vs), 951(s), 876(s), 787(m), 616(w), 531(w), 380(w). intensity data for compound 1 was measured on a Rigaku R-AXIS RAPID IP

SC R

diffractometer with graphite monochromated Mo Kα ( λ = 0.71073 Å) radiation. Crystals showed no evidence of crystal decay during data collections. Structures were solved by direct methods

NU

and refined using the full-matrix least squares on F2 using SHELXTL-97 crystallographic software package. All non-hydrogen atoms of compound 1 was refined anisotropically.

MA

Hydrogen atoms of compound 1 was set in calculated positions and refined with a riding mode. A summary of the crystallographic data and structure refinements for compounds 1: empirical

D

formula: C14H65Cu3.5W9.5N14O46.5V5.5, formula weight: 3422.80, crystal system: orthorhombic,

TE

space group: Pccn, a = 48.05(2) Å, b = 13.381(7) Å, c = 20.379(10) Å, α = β = γ = 90 º, V = 13102(12) Å3, Z = 8, Dc = 3.471 kg/m3, absorption coefficient: 18.557 mm-1, F(000) = 12400,

EP

theta range for data collection: 1.58º to 26.00º, Reflections collected/unique: 32671 / 12587,

AC C

R(int) = 0.0705, Goodness-of-fit on F2: 1.022, R1 (I>Σ(I)) = 0.0512, ωR2 (all data) = 0.1470. CCDC number: 993625; The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif. [37] I.D.

Brown, In Structure and Bonding in Crystals (Eds.: M. O’Keefe, A. Navrotsky), Academic

press, New York, 1981, vol. 2, pp. 1-30. [38] G.M.

Varga Jr., E. Papaconstantinou, M.T. Pope, Heteropoly blues. IV. Spectroscopic and

magnetic properties of some reduced polytungstates, Inorg. Chem. 9 (1970) 662-667. [39] R.A.

Prados, M.T. Pope, Low-temperature electron spin resonance spectra of heteropoly blues

derived from some 1:12 and 2:18 molybdates and tungstates, Inorg. Chem. 15 (1976) 2547-2553. [40] M.T.

Pope, A Müller, Polyoxometalate Chemistry: An Old Field with New Dimensions in

Several Disciplines, Angew. Chem., Int. Ed. Eng. 30 (1991) 34-38.

12

ACCEPTED MANUSCRIPT [41] N.

Casañ-Pastor, L.C.W. Baker, Magnetic properties of mixed-valence heteropoly blues.

IP T

Interactions within complexes containing paramagnetic atoms in various sites as well as "blue" electrons delocalized over polytungstate frameworks, J. Am. Chem. Soc. 114 (1992)

Khan, S. Cevik, R.J. Doedens, Q. Chen, S. Li, C.J. O’Connor, Hydrothermal synthesis and

characterization

of

mixed-valence

hexatungstates:

crystal

structures

of

NU

[42] M.I.

SC R

10384-10394, and references therein.

[(C2H5)4N]3[WVW5VIO19]·0.5H2O and [H3N(CH2)2NH3]2 [WVW5VIO19]·[H2N(CH2)2NH2]Cl

EP

TE

D

Kahn, Molecular magnetism, VCH, New York, 1993.

AC C

[43] O.

MA

·8H2O, Inorg. Chem. Acta. 277 (1998) 69-75.

13

ACCEPTED MANUSCRIPT Figure captions:

IP T

Fig.1. Ball/stick representation of the bi-capped Keggin polyoxoanion supporting one transition metal complexes of 1 (M9 = 0.25W+0.75V, M10 = 0.25W+0.75V, M11 = 0.5W+0.5V and

SC R

M12 = 0.5W+0.5V).

Fig.2. The [Cu(4)(en)]2+ cations join neighboring left- and right-handed helical 1D chains into a new

NU

2D layer through Cu-O covalent interactions in the ab plane, [Cu(en)2(H2O)]2+ balance cations,

MA

H2O molecules and past en molecules have been omitted for clarity. Fig.3. (a) View of 3-D supramolecular network structure with hydrogen bonding interactions

D

between water molecules and oxygen atoms from two neighbouring 2-D layers along the

TE

given directions. Several hydrothen atoms are omitted for clarity. (b) Schematic view of 2-D

EP

layer in 1. (c) Schematic drawing of the 3-D supramolecular topology in 1 Fig.4. Temperature dependences of the reciprocal magnetic susceptibility χm-1 and the product µeff for

AC C

compound 1.

14

AC C

EP

TE

D

MA

NU

SC R

IP T

ACCEPTED MANUSCRIPT

Fig.1. Ball/stick representation of the bi-capped Keggin polyoxoanion supporting one transition metal complexes of 1 (M9 = 0.25W+0.75V, M10 = 0.25W+0.75V, M11 = 0.5W+0.5V and M12 = 0.5W+0.5V).

15

EP

TE

D

MA

NU

SC R

IP T

ACCEPTED MANUSCRIPT

AC C

Fig.2. The [Cu(4)(en)]2+ cations join neighboring left- and right-handed helical 1D chains into a new 2D layer through Cu-O covalent interactions in the ab plane, [Cu(en)2(H2O)]2+ balance cations, H2O molecules and past en molecules have been omitted for clarity.

16

AC

CE

PT

ED

MA

NU

SC

RI P

T

ACCEPTED MANUSCRIPT

Fig.3. (a) View of 3-D supramolecular network structure with hydrogen bonding interactions between water molecules and oxygen atoms from neighbouring 2-D layers along the given directions. Several hydrothen are omitted for clarity. (b) Schematic view of 2-D layer in 1. (c) Schematic drawing of the 3-D supramolecular topology in 1

17

IP T

ACCEPTED MANUSCRIPT

4.1

NU

100

4.0

MA

80 60

3.9 3.8

D

40 20 0 50

100

AC C

EP

0

TE

-1

120

4.2

150

eff (B)

140

m (mol/emu)

4.3

SC R

160

3.7 200

250

300

3.6

Temperature (K)

Fig.4. Temperature dependences of the reciprocal magnetic susceptibility χm-1 and the product µeff for compound 1.

18

ACCEPTED MANUSCRIPT

IP T

A novel 2D network constructed from copper complexes and bi-capped tungsten-based Keggin clusters

a

SC R

Ya-Bing Liu,a,b Li-Wei Fu,a Wei-Jie Duan,a Li-Na Xiao,a Yang-Yang Hu,a De-Chuan Zhao,a Hai-Yang Guo,a Xiao-Bing Cui,a* Ji-Qing Xu,a Department of Chemistry, Collage of Chemistry and State Key Laboratory of Inorganic

Synthesis and Preparative Chemistry. Jilin University, Changchun 130023, China Department of Materials Science and Engineering, Jilin Jianzhu University, Changchun,

NU

b

MA

130118, China

AC C

EP

TE

D

Corresponding author: Xiao-Bing Cui, E-mail: [email protected], tel: 86-431-88499132.

Graphical abstract - pictogram

19

ACCEPTED MANUSCRIPT

new

mono-supporting

bi-capped

Keggin

SC R

A

IP T

Graphical abstract - synopsis

heteropolytungstovanadate,

[Cu(en)2(H2O)]{[Cu0.5(en)]3[VVW6.5VIW3VV4.5IVO42Cu(en)2]}·3.5H2O (1) (en = ethylenediamine), has been synthesized under hydrothermal method. Compound 1 exhibits a novel 2-D structure

NU

containing unusual 1-D infinite left- and right-handed helical chains linked by transition metal coordination fragment. The adjacent layers are further interconnected into a 3-D supramolecular

AC C

EP

TE

D

MA

structure via hydrogen bonds.

20

ACCEPTED MANUSCRIPT Highlights: New bi-capped tungsten-based Keggin anion [VVWVI6.5WV3VIV4.5O42]7-.

2.

2-D layer structure formed by bi-capped tungsten-based Keggin anions and TMCs.

3.

Compound 1 shows antiferromagnetic interactions.

AC C

EP

TE

D

MA

NU

SC R

IP T

1.

21