In situ Hydrothermal Synthesis, Crystal Structure and Fluorescence Properties of Two Cadmium Coordination Polymers†

doi:10.7503/cjcu20170261

Abstract

Abstract:

Two coordination polymers(CPs) based on cadmium chlorate and the ligand H₂PPDA(H₂PPDA=pyrazin[2,3-f][1,10] phenanthroline-2,3-dicarboxylic acid) were prepared under hydrothermal conditions. The ligand H₂PPDA decomposed into Dpq(Dpq= dipyrido[3,2-d:2',3'-f]quinoxaline) through in situ reaction. CPs 1 and 2 have the same molecular formula [Cd(Dpq)Cl₂] but different structures. CPs 1 and 2 are two-dimensional supramolecular networks formed by one-dimensional chains through strong π-π stacking among aromatic ring ligands. Furthermore, CP 1 shows good fluorescence properties in the solid state at room temperature.

Key words: In situ reaction, Hydrothermal synthesis, π-π Stacking;, Fluorescence, Cadmium coordination polymer

CLC Number:

O614

TrendMD:

SONG Wei, WANG Liqun, ZENG Shuangli, WANG Li, FAN Yong, XU Jianing. In situ Hydrothermal Synthesis, Crystal Structure and Fluorescence Properties of Two Cadmium Coordination Polymers^†[J]. Chem. J. Chinese Universities, 2018, 39(7): 1406.

Figures/Tables 11

References 34

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Compound	1	2
Empirical formula	C₁₄H₈Cl₂N₄Cd	C₁₄H₈Cl₂N₄Cd
Formula weight	415.54	415.54
Crystal system	Monoclinic	Orthorhombic
Space group	C2/c	Cmcm
a/nm	1.6577(2)	1.5788(3)
b/nm	1.28344(17)	1.2109(2)
c/nm	0.71515(9)	0.69497(14)
α/(°)	90	90
β/(°)	112.901(2)	90
γ/(°)	90	90
Volume/nm³	1.4016(3)	1.3286(4)
Z	4	4
Calculated density(Mg·m^-3)	1.969	2.077
Absorption coefficient/mm^-1	1.935	2.041
F(000)	808	808
θ range/(°)	32.07—28.31	3.36—27.43
Goodness-of-fit on F²	1.1067	1.111
R₁,wR₂ [I>2σ(I)]^*	R₁=0.0279, wR₂=0.0754	R₁=0.0260, wR₂=0.0875
R₁,wR₂(all data)^*	R₁=0.0329, wR₂=0.0784	R₁=0.0271, wR₂=0.0882

Compound	1	2
Empirical formula	C₁₄H₈Cl₂N₄Cd	C₁₄H₈Cl₂N₄Cd
Formula weight	415.54	415.54
Crystal system	Monoclinic	Orthorhombic
Space group	C2/c	Cmcm
a/nm	1.6577(2)	1.5788(3)
b/nm	1.28344(17)	1.2109(2)
c/nm	0.71515(9)	0.69497(14)
α/(°)	90	90
β/(°)	112.901(2)	90
γ/(°)	90	90
Volume/nm³	1.4016(3)	1.3286(4)
Z	4	4
Calculated density(Mg·m^-3)	1.969	2.077
Absorption coefficient/mm^-1	1.935	2.041
F(000)	808	808
θ range/(°)	32.07—28.31	3.36—27.43
Goodness-of-fit on F²	1.1067	1.111
R₁,wR₂ [I>2σ(I)]^*	R₁=0.0279, wR₂=0.0754	R₁=0.0260, wR₂=0.0875
R₁,wR₂(all data)^*	R₁=0.0329, wR₂=0.0784	R₁=0.0271, wR₂=0.0882

Cd1—N1#1	0.23553(2)	Cd1—N1	0.23553(2)	Cd1—Cl1#1	0.25315(7)
Cd1—Cl1	0.25315(7)	Cd1—Cl1#2	0.27349(8)	Cd1—Cl1#3	0.27349(8)
Cl1—Cd1#3	0.27349(8)
N1#1—Cd1—Cl1#1	93.65(6)	N1—Cd1—Cl1#1	160.63(6)	Cl1#1—Cd1—Cl1#3	96.40(3)
N1#1—Cd1—Cl1	160.63(6)	N1—Cd1—Cl1	93.65(6)	Cl1#2—Cd1—Cl1#3	177.18(3)
Cl1#1—Cd1—Cl1	103.97(4)	N1#1—Cd1—Cl1#2	92.96(6)	Cl1—Cd1—Cl1#2	96.40(3)
N1—Cd1—Cl1#2	84.73(6)	Cl1#1—Cd1—Cl1#2	85.35(2)	N1—Cd1—Cl1#3	92.96(6)
N1#1—Cd1—N1	70.33(11)	N1#1—Cd1—Cl1#3	84.73(6)	Cl1—Cd1—Cl1#3	85.35(2)

Cd1—N1#1	0.23553(2)	Cd1—N1	0.23553(2)	Cd1—Cl1#1	0.25315(7)
Cd1—Cl1	0.25315(7)	Cd1—Cl1#2	0.27349(8)	Cd1—Cl1#3	0.27349(8)
Cl1—Cd1#3	0.27349(8)
N1#1—Cd1—Cl1#1	93.65(6)	N1—Cd1—Cl1#1	160.63(6)	Cl1#1—Cd1—Cl1#3	96.40(3)
N1#1—Cd1—Cl1	160.63(6)	N1—Cd1—Cl1	93.65(6)	Cl1#2—Cd1—Cl1#3	177.18(3)
Cl1#1—Cd1—Cl1	103.97(4)	N1#1—Cd1—Cl1#2	92.96(6)	Cl1—Cd1—Cl1#2	96.40(3)
N1—Cd1—Cl1#2	84.73(6)	Cl1#1—Cd1—Cl1#2	85.35(2)	N1—Cd1—Cl1#3	92.96(6)
N1#1—Cd1—N1	70.33(11)	N1#1—Cd1—Cl1#3	84.73(6)	Cl1—Cd1—Cl1#3	85.35(2)

Cd1—N1#1	0.23874(3)	Cd1—N1	0.23874(3)	Cd1—Cl1#2	0.26266(8)
Cd1—Cl1#3	0.26266(8)	Cd1—Cl1#4	0.26266(8)	Cd1—Cl1	0.26266(8)
Cl1—Cd1#3	0.26266(8)
N1#1—Cd1—Cl1#2	132.38(4)	N1—Cd1—Cl1#2	86.67(6)	Cl1#2—Cd1—Cl1	82.82(3)
N1#1—Cd1—Cl1#3	86.67(6)	N1—Cd1—Cl1#3	132.38(4)	Cl1#4—Cd1—Cl1	136.27(2)
Cl1#2—Cd1—Cl1#3	136.27(2)	N1#1—Cd1—Cl1#4	86.67(6)	N1—Cd1—Cl1#4	132.38(4)
Cl1#3—Cd1—Cl1	81.23(4)	Cl1#2—Cd1—Cl1#4	81.23(4)	Cl1#3—Cd1—Cl1#4	82.82(3)
N1#1—Cd1—N1	68.42(16)	N1#1—Cd1—Cl1	132.38(4)	N1—Cd1—Cl1	86.67(6)