Syntheses, Structures and Catalytic Properties of Two Supramolecular Complexes Based on 2-Pyridylamine and Cluster †

doi:10.7503/cjcu20190642

Abstract

Abstract:

Two new supramolecular complexes, [H₃PMo₁₂O₄₀]₂[C₅H₆N₂]₆(1) and [H₂PMo₁₂V₂O₄₂]·[C₅H₆N₂]₅·3H₂O(2)(C₅H₆N₂=2-pyridylamine), were synthesized and characterized by means of elemental analysis, infrared spectroscopy(FTIR), UV-Vis spectrum(UV-Vis), X-ray photoelectron spectroscopy(XPS), thermal gravimetric(TG) analysis, power X-ray diffraction(PXRD) and single-crystal X-ray diffraction analysis. Both of compounds 1 and 2 consisting of different clusters were assembled into 3D inorganic supramoleculae network with different packing modes. In addition, the catalytic properties of two complexes were investigated using the epoxidation of styrene.

Key words: Polyoxomatelate, Supramolecular compound, 2-Pyridylamine, Hydrothermal synthesis, Catalytic property

CLC Number:

O614
O643

TrendMD:

LIU Yabing,LI Mingyang,TIAN Ge,ALATENG Shaga,PEI Tonghe,NIE Jingsi. Syntheses, Structures and Catalytic Properties of Two Supramolecular Complexes Based on 2-Pyridylamine and Cluster ^†[J]. Chem. J. Chinese Universities, 2020, 41(5): 995.

Figures/Tables 7

Complex	1	2
Empirical formula	C₃₀H₄₂Mo₂₄N₁₂O₈₀P₂	C₂₅H₃₈Mo₁₂N₁₀O₄₅PV₂
Formula weight	4215.68	2482.99
Crystal system	Triclinic	Monoclinic
Space group	P $1 ˉ$	P2₁/c
a/nm	0.99506(3)	2.10578(8)
b/nm	1.17367(5)	1.29659(4)
c/nm	1.92973(5)	2.51313(8)
α/(°)	88.359(3)	90
β/(°)	86.542(3)	117.802(8)
γ/(°)	81.378(3)	90
Volume/nm³	2.22371(2)	6.0696(4)
Z	1	4
D_c/(g·cm^-3)	3.148	2.717
μ/mm^-1	3.419	2.819
θ range/(°)	2.88—27.00	2.27—25.05
Limiting indices	-12≤h≤12, -14≤k≤14, -24≤l≤16	-25≤h≤25, -15≤k≤15, -29≤l≤29
F(000)	1984	4732
Crystal size	0.22 mm×0.21 mm×0.19 mm	0.25 mm×0.23 mm×0.20 mm
Reflection collected/Independent	18092/9533	65284/10743
Goodness-of-fit on F²	1.058	1.057
Final R indices [I>2σ(I)]	R₁=0.0546, wR₂=0.1101	R₁=0.0598, wR₂=0.1825
R indices(all data)	R₁=0.0690, wR₂=0.1165	R₁=0.0701, wR₂=0.1952

Complex	1	2
Empirical formula	C₃₀H₄₂Mo₂₄N₁₂O₈₀P₂	C₂₅H₃₈Mo₁₂N₁₀O₄₅PV₂
Formula weight	4215.68	2482.99
Crystal system	Triclinic	Monoclinic
Space group	P $1 ˉ$	P2₁/c
a/nm	0.99506(3)	2.10578(8)
b/nm	1.17367(5)	1.29659(4)
c/nm	1.92973(5)	2.51313(8)
α/(°)	88.359(3)	90
β/(°)	86.542(3)	117.802(8)
γ/(°)	81.378(3)	90
Volume/nm³	2.22371(2)	6.0696(4)
Z	1	4
D_c/(g·cm^-3)	3.148	2.717
μ/mm^-1	3.419	2.819
θ range/(°)	2.88—27.00	2.27—25.05
Limiting indices	-12≤h≤12, -14≤k≤14, -24≤l≤16	-25≤h≤25, -15≤k≤15, -29≤l≤29
F(000)	1984	4732
Crystal size	0.22 mm×0.21 mm×0.19 mm	0.25 mm×0.23 mm×0.20 mm
Reflection collected/Independent	18092/9533	65284/10743
Goodness-of-fit on F²	1.058	1.057
Final R indices [I>2σ(I)]	R₁=0.0546, wR₂=0.1101	R₁=0.0598, wR₂=0.1825
R indices(all data)	R₁=0.0690, wR₂=0.1165	R₁=0.0701, wR₂=0.1952

Compound	Hydrogen bond	d(D—H…A)/nm	Compound	Hydrogen bond	d(D—H…A)/nm
1	O16…O17(#1)	0.2862(9)	2	O_W3…O28(#2)	0.2928(1)
	O23…O37(#2)	0.3183(1)		C13—H…O11(#1)	0.3016(1)
	O43…O15(#4)	0.3167(1)		N5—H…O_W3	0.3218(3)
	N3—H…O15	0.3177(1)		N3—H…O13(#3)	0.3344(1)
	N5—H…O39(#6)	0.3020(1)		N4—H…O_W2(#2)	0.3142(6)
	C3—H…O28(#7)	0.3145(1)		C13—H…O11(#1)	0.3016(1)
	O23…O30(#2)	0.3171(1)		O11…O41(#1)	0.3037(4)
	O24…O37	0.3183(2)		O_W1…O_W3(#2)	0.3186(1)
	O39…O36(#3)	0.3154(1)		O_W2…O5(#2)	0.3157(1)
	N2—H…O13(#5)	0.3204(2)		O_W1…O33(#2)	0.2891(1)
	C1—H…O36(#6)	0.3223(1)		N1—H…O8	0.3273(1)
	C9—H…O25	0.3321(2)		N2—H…O5	0.3064(1)
2	O11…O31(#1)	0.2935(1)		C6—H…O27(#2)	0.3059(1)
	O13…O21(#1)	0.3125(1)		C10—H…O21(#2)	0.3213(1)
	O_W2…O_W3	0.3218(1)		C15—H…O14(#2)	0.3203(3)

Catalyst	Styrene conversion(%)	Product selectivity(%)
Catalyst	Styrene conversion(%)	So	Bza	Other
Compound 1	25.9	62.8	34.3	2.8
Compound 2	35.3	74.0	20.8	5.2
Compound 3^[20]	76.7	55.3	34.3	10.4
Compound 4^[25]	86.9	64.8	30.5	4.7
Compound 5^[26]	21.0	2.5	96	1.3

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