Synthesis and Characterization of a 2D Tungstovanadated Derivative: [Cu(en)2]2[VⅤO44{Cu(en)2(H2O)}2]·3H2O†

doi:10.7503/cjcu20140763

Abstract

Abstract:

A new compound, [Cu(en)₂]₂[V^ⅤO₄₄{Cu(en)₂(H₂O)}₂]·3H₂O(1, en=ethy-lenediamine), was hydrothermally synthesized and characterized by elemental analysis, Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS), electron paramagnetic resonance(ESR), X-ray diffraction analysis(XRD), thermogravimetric(TG) analysis and single-crystal X-ray diffraction analysis. Compound 1 represents a 2D layer structure constructed from tetra-capped bi-supporting Keggin tungstovanadates and transition metal complexes. Adjacent layers are further interconnected into a 3D supramolecular structure via hydrogen bonds. The magnetic susceptibility of compound 1 demonstrates the presence of ferromagnetic interactions. In addition, the photocatalytic activity of compound 1 for the phtodegradation of Rhodamine B(RhB) was also investigated.

Key words: Hydrothermal synthesis, Tungstovanadate, Magnetic property, Photocatalytic activity

CLC Number:

O611

TrendMD:

LIU Yabing, DUAN Weijie, CUI Xiaobing, XU Jiqing. Synthesis and Characterization of a 2D Tungstovanadated Derivative: [Cu(en)₂]₂[V^ⅤO₄₄{Cu(en)₂(H₂O)}₂]·3H₂O^†[J]. Chem. J. Chinese Universities, 2015, 36(1): 34.

Figures/Tables 13

Table 1 Crystal data and structure refinement for compound 1

Empirical formula	C₁₆W_6.5N₁₆Cu₄O₄₉V_10.5	D/(Mg·m^-3)	2.949
Formula weight	3258.86	μ/mm^-1	12.633
Crystal system	Triclinic	Limiting indices	-14≤h≤17
Space group	P		-15≤k≤17
a/nm	1.2857(2)		-15≤l≤18
b/nm	1.3064(2)	F(000)	1513
c/nm	1.3951(3)	Crystal size	0.24 mm×0.22 mm×0.21 mm
α/(°)	81.324(1)	Goodness-of-fit on F²	1.041
β/(°)	63.094(1)	Final R indices[I>2σ(I)]^*	R₁=0.0570
γ/(°)	65.150(1)		wR₂ = 0.1615
Volume/nm³	1.8354(6)	R indices(all data)	R₁ = 0.0972
Z	1		wR₂ = 0.1797

Table 2 Selected bond lengths(nm) and bond angles(°) for compound 1

W1/V1—O10	0.1688(8)	W1/V1—O8	0.1845(9)	W2/V2—O5	0.1804(9)
W2/V2—O12	0.2031(9)	W3/V3—O18	0.1884(8)	W3/V3—O4	0.2443(1)
W4/V4—O20	0.1683(8)	W5/V5—O9	0.1876(9)	W6/V6—O18	0.1989(9)
V7—O2	0.1689(2)	V7—O3	0.1666(1)	V8—O12	0.1936(9)
V9—O22	0.1913(9)	V9—O18	0.1977(1)	Cu1—N2	0.2004(1)
Cu2—N5	0.1978(1)	Cu3—N7	0.1999(2)	N6—C6	0.146(2)
O4—V7—O1	111.0(7)	O2—V7—O1	109.4(7)	V7—O1—W2/V2	119.8(6)
V8—O23—W1/V1	101.8(4)	C8—C7—N7	104.0(2)	V9—O22—W5/V5	101.6(4)

Fig.1 Ball/strick representation of the tetra-capped Keggin polyoxoanion supporting two transition metal complex of compound 1 M1, M2: 0.8W+0.2V; M3, M4: 0.46W+0.54V; M5, M6: 0.36W+0.64V.

Fig.2 [Cu(en)2]2+ cations join polyoxoanion into 2D layer through Cu—O interactions [Cu1(en)2(H2O)]2+ cations, water and en molecules are omitted for clarity.

Fig.3 View of 3D supramolecular network structure with hydrogen bonding interactions between water molecules and oxygen atoms from two neighboring 2D layers along b axix(A) and schematic drawing of the 3D supramolecular topology in compound 1(B) (A) Several hydrogen atoms are omitted for clarity; (B) covalent bond and weak bond are shown with two-colored lines, and hydrogen bonds are shown with purple lines, respectively.

Fig.4 FTIR spectrum of compound 1

Fig.5 XPS spectra for W(A) and V(B) elements of compound 1

Fig.6 EPR spectrum of compound 1

Fig.7 XRD patterns of compound 1

Fig.8 TG curve of compound 1

Fig.9 Temperature dependences of the reciprocal magnetic susceptibility and the product μeff for compound 1

Fig.10 Changes of UV-Vis absorption spectra of RhB solutions with compound 1 Irradiation time(min) from a to m: 0, 30, 60, 90, 120, 150, 180, 210, 240, 270, 300, 330, 360.

Fig.11 Photocatalytic activities of compound 1 for the degradation of RhB under UV light a. In the presence of compound 1; b. without compound 1.

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Synthesis and Characterization of a 2D Tungstovanadated Derivative: [Cu(en)₂]₂[V^ⅤO₄₄{Cu(en)₂(H₂O)}₂]·3H₂O^†

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