Syntheses, Structures and Photocatalytic Activities of Coordinated Supramolecular Complexes Containing Triazin-pyrazole Ligand†

doi:10.7503/cjcu20150099

Abstract

Abstract:

In the mixture of ethanol and water, two complexes [Co(Bpz*eaT)(H₂O)₃]·2H₂BTC·2H₂O(1) and [Cu(Bpz*eaT)(H₂O)₃]·2H₂BTC·CH₃CH₂OH·H₂O(2) were designed and synthesized via the reaction of metal salts and ligands H₃BTC(benzene-1,3,5-tricarboxylic acid) and Bpz*eaT[2,4-bis(3,5-dimethylpyrazol-1-yl)-6-diethylamino-1,3,5-triazine]. The complexes were characterized by elemental analysis, IR spectrometry, UV-Vis spectrometry, thermal gravimetric analysis, X-ray powder and X-ray single crystal diffraction analysis. Structural analysis reveals that both complexes 1 and 2 form distorted octahedral geometry, and complex 1 has a 3D network structure and complex 2 has a 2D layer structure via hydrogen bonding connection. Furthermore, the photocatalytic performances of complexes 1 and 2 were studied and the result revealed that the photocatalytic activity of complex 1 was better than that of complex 2.

Key words: Cobalt/Copper complex, Triazin-pyrazole Ligand, Supramolecule, Crystal structure, Photocatalytic activity

CLC Number:

O614

TrendMD:

WANG Zhinan, WANG Jixiao, SONG Jian, GAO Xue, FENG Xiaodong, SUN Lixian, XING Yongheng. Syntheses, Structures and Photocatalytic Activities of Coordinated Supramolecular Complexes Containing Triazin-pyrazole Ligand^†[J]. Chem. J. Chinese Universities, 2015, 36(8): 1478.

Figures/Tables 7

Table 1 Crystal data and structure refinements for complexes 1 and 2

Complex	1	2
Formula	C₃₅H₄₄N₈O₁₇Co	C₃₇H₄₈N₈O₁₇Cu
Molecular weight	907.71	940.37
Crystal system	Orthorhombic	Orthorhombic
Space group	P2₁2₁2₁	P2₁2₁2₁
a/nm	1.3575(1)	1.3549(8)
b/nm	1.7271(1)	1.7182(9)
c/nm	1.8297(1)	1.8201(10)
α/(°)	90	90
β/(°)	90	90
γ/(°)	90	90
V/nm³	4.2897(5)	4.237(4)
Z	4	4
D_calc/(g·cm^-3)	1.406	1.474
F(000)	1892	1964
μ(Mo Kα)/mm^-1	0.480	0.599
θ range/(°)	1.62—28.45	1.87—28.25
Reflections collected	36042	26235
Independent reflections[I>2σ(I)]	6578	7551
Parameters	560	573
Goodness of fit	1.015	1.028
R^a	0.0688(0.1207)^b	0.0674(0.0935)^b
w $R 2 a$	0.1849(0.2187)^b	0.1709(0.1895)^b

Table 1 Crystal data and structure refinements for complexes 1 and 2

Complex	1	2
Formula	C₃₅H₄₄N₈O₁₇Co	C₃₇H₄₈N₈O₁₇Cu
Molecular weight	907.71	940.37
Crystal system	Orthorhombic	Orthorhombic
Space group	P2₁2₁2₁	P2₁2₁2₁
a/nm	1.3575(1)	1.3549(8)
b/nm	1.7271(1)	1.7182(9)
c/nm	1.8297(1)	1.8201(10)
α/(°)	90	90
β/(°)	90	90
γ/(°)	90	90
V/nm³	4.2897(5)	4.237(4)
Z	4	4
D_calc/(g·cm^-3)	1.406	1.474
F(000)	1892	1964
μ(Mo Kα)/mm^-1	0.480	0.599
θ range/(°)	1.62—28.45	1.87—28.25
Reflections collected	36042	26235
Independent reflections[I>2σ(I)]	6578	7551
Parameters	560	573
Goodness of fit	1.015	1.028
R^a	0.0688(0.1207)^b	0.0674(0.0935)^b
w $R 2 a$	0.1849(0.2187)^b	0.1709(0.1895)^b

Fig.1 Molecular structure of complex 1(A) and views of two 1D chains(B), 2D sheet(C) and 3D network(D) in complex 1The atoms from Bpz*eaT except those coordinating with metal and the H atoms except those forming the hydrogen bonds are omitted for clarity.

Fig.2 Molecular structure of complex 2(A), view of connected method of two H2BTCs(B), 1D chain(C) and 2D sheet(D) of hydrogen bonding in complex 2 All atoms from Bpz*eaT except for coordinated with metal and all H atoms except for the hydrogen bonds are omitted for clarity.

Fig.3 (Ahν)2-hν plots of complexes 1 and 2

Fig.4 UV-Vis absorption spectra of RhB aqueous solutions using complex 1(A) and 2(B) as photocatalyst, respectively

Fig.5 Degradation curves of RhB using different photocatalystsa. Without photocatalyst; b. with complex 1; c. with complex 2.

Fig.6 Schematic illustration for the photocatalytic mechanism

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