二维钨-钒簇聚物[Cu(en)2]2·[VⅤO44{Cu(en)2(H2O)}2]·3H2O的合成与表征

doi:10.7503/cjcu20140763

摘要/Abstract

摘要：

采用水热法合成了一个钨-钒簇聚物[Cu(en)₂]₂[V^Ⅴ{Cu(en)₂(H₂O)}₂]·3H₂O(1, en=乙二胺), 并通过X射线单晶衍射、元素分析、傅里叶变换红外光谱、 X射线粉末衍射、热重分析、价键计算、 X射线光电子能谱、电子顺磁共振和磁性分析对其结构和性能进行了表征. 结果表明, 化合物1是以双支撑的四帽Keggin结构 [(V^ⅤO₄){Cu(en)₂(H₂O)}₂]^4- 钨-钒簇合物阴离子为基本结构单元, 与4个[Cu(en)₂]²⁺配合物阳离子以共价键和弱键相连接形成二维层状结构, 相邻层又通过氢键连接成三维超分子网络. 研究了化合物1的磁性及光催化降解罗丹明B的活性.

关键词: 水热合成, 钨-钒簇, 磁性, 光催化活性

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

中图分类号:

O611

TrendMD:

刘亚冰, 段为杰, 崔小兵, 徐吉庆. 二维钨-钒簇聚物[Cu(en)₂]₂·[V^ⅤO₄₄{Cu(en)₂(H₂O)}₂]·3H₂O的合成与表征. 高等学校化学学报, 2015, 36(1): 34.

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^†. Chem. J. Chinese Universities, 2015, 36(1): 34.

图/表 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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二维钨-钒簇聚物[Cu(en)₂]₂·[V^ⅤO₄₄{Cu(en)₂(H₂O)}₂]·3H₂O的合成与表征

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

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