Synthesis, Characterization and Blue-emission of Cd(Ⅱ)Coordination Polymers with μ-Chlorine-Bridging One-dimensional Chain Structures†

doi:10.7503/cjcu20140986

Abstract

Abstract:

Two coordination polymers, {[Cd(mpep)]Cl₂}_n(1, mpep=2-{1-[(2-methylphenyl)imino]-ethyl}pyridine) and {[Cd(acpy)]Cl₂}_n(2, acpy=2-acetylpyridine), were synthesized under solvothermal condition. The structures of complexes 1 and 2 were characterized by single crystal X-ray diffraction analysis, ¹H nuclear magnetic resonance(¹H NMR) spectrometry, elemental analysis and infrared(IR) spectrometry. The results show that both complexes 1 and 2 have 1D chain structure. The central cadmium(Ⅱ) atom in complex 1 is coordinated by four chloride ions and two nitrogen atoms from mpep, forming a distorted cis-octahedron coordination geometry, and the Cd(mpep)]Cl₂ unit builds up a polymeric chain by μ₂-chlorine-bridging. The central cadmium(Ⅱ) atom in complex 2 is coordinated by a nitrogen atom and an oxygen atom from acpy and four chloride ions, forming a distorted cis-octahedron coordination geometry, the Cd(acpy)]Cl₂ unit builds up a polymeric chain by μ₂-chlorine-bridging. Additionally, the fluorescent properties of the two complexes were characterized in both solid state and in different polar solvents. The results show that com-plexes 1 and 2 exhibit blue fluorescence emission(ca.390—433 nm) in CH₃OH, CH₃CN and CH₂Cl₂, indicating that the coordination polymers have weak solvent effect. The emission spectra of complexes 1 and 2 at 298 K are centered at 440 and 473 nm respectively in solid state. Comparing to the emission spectra in solutions, the emission spectra in solid-state undergo obvious red-shift. The lifetime of complexes 1 and 2 are relatively long(ca.19.08—60.20 μs) at room temperature.

Key words: Cadmium complex, Schiff base, Blue-emission property, Fluorescence lifetime

CLC Number:

O613

TrendMD:

HUANG Jian, LIU Zhigang, FAN Ruiqing, DONG Yuwei, ZHANG Huijie, WANG Yulei, YANG Yulin. Synthesis, Characterization and Blue-emission of Cd(Ⅱ)Coordination Polymers with μ-Chlorine-Bridging One-dimensional Chain Structures^†[J]. Chem. J. Chinese Universities, 2015, 36(3): 411.

Figures/Tables 13

Scheme 1 Synthetic route of mpep ligand

Table 1 Crystal data and refinement parameters of complexes 1 and 2

Complex	1	2
Formula	C₁₄H₁₄CdCl₂N₂	C₇H₇CdCl₂NO
Molecular weight	393.58	304.45
Crystal system	Triclinic	Triclinic
Space group	P $1 ˉ$	P $1 ˉ$
a/nm	0.7493(1)	0.7264(2)
b/nm	0.9586(1)	0.8328(2)
c/nm	1.0492(1)	0.9328(1)
α/(°)	91.858(2)	109.49(2)
β/(°)	102.787(2)	94.30(1)
γ/(°)	92.890(2)	114.36(3)
Volume/nm³	0.7333(1)	0.4695(1)
Z	2	2
T/K	298	298
D_c/(g·cm^-3)	1.783	2.154
μ/mm^-1	1.840	2.843
F(000)	388	292
θ_range	1.99° to 25.00°	3.73° to 27.56°
Number of reflections collected	5186(R_int=0.0265)	2763(R_int=0.0235)
Number of independent reflections	2560	2134
Number of data/restraints/parameters	2560/0/172	2134/0/110
GOF	1.081	0.997
R^*[I >2σ(I)]	R₁=0.0327, wR₂=0.0840	R₁=0.0313, wR₂=0.0709

Table 1 Crystal data and refinement parameters of complexes 1 and 2

Complex	1	2
Formula	C₁₄H₁₄CdCl₂N₂	C₇H₇CdCl₂NO
Molecular weight	393.58	304.45
Crystal system	Triclinic	Triclinic
Space group	P $1 ˉ$	P $1 ˉ$
a/nm	0.7493(1)	0.7264(2)
b/nm	0.9586(1)	0.8328(2)
c/nm	1.0492(1)	0.9328(1)
α/(°)	91.858(2)	109.49(2)
β/(°)	102.787(2)	94.30(1)
γ/(°)	92.890(2)	114.36(3)
Volume/nm³	0.7333(1)	0.4695(1)
Z	2	2
T/K	298	298
D_c/(g·cm^-3)	1.783	2.154
μ/mm^-1	1.840	2.843
F(000)	388	292
θ_range	1.99° to 25.00°	3.73° to 27.56°
Number of reflections collected	5186(R_int=0.0265)	2763(R_int=0.0235)
Number of independent reflections	2560	2134
Number of data/restraints/parameters	2560/0/172	2134/0/110
GOF	1.081	0.997
R^*[I >2σ(I)]	R₁=0.0327, wR₂=0.0840	R₁=0.0313, wR₂=0.0709

Table 2 Selected bond distances(nm) and bond angles(°) of complexs 1*

Cd1—N1	0.2347(4)	Cd1—Cl1	0.2667(1)	Cd1—Cl2	0.2500(1)
Cd1— N2	0.2404(3)	Cd1—Cl1#1	0.2606(1)	Cd1—Cl2#2	0.2866(1)
N1—Cd1—N2	69.40(3)	Cl2—Cd1—Cl1#1	101.14(4)	N1—Cd1—Cl2#2	78.86(1)
N1—Cd1—Cl2	157.42(1)	N1—Cd1—Cl1	96.92(1)	N2—Cd1—Cl2#2	90.99(9)
N2—Cd1—Cl2	102.89(9)	N2—Cd1—Cl1	84.73(9)	Cl2—Cd1—Cl2#2	80.13(4)
N1—Cd1—Cl1#1	90.67(9)	Cl2—Cd1—Cl1	103.58(4)	Cl1#1—Cd1—Cl2#2	100.28(4)
N2—Cd1—Cl1#1	154.87(9)	Cl1#1—Cd1—Cl1	82.62(4)	Cl1—Cd1—Cl2#2	174.85(4)

Fig.1 Molecular structure(A), coordination geometry of Cd1 ion(B) and the 1D chain of complex 1(C)

Fig.2 Intermolecular(A) and intramolecular(B) hydrogen bonds in complex 1 and supramolecular structure of complex 1(C) Hydrogen bonds are illustrates by dashed lines.

Table 3 Hydrogen bond lengths and bond angles of complex 1

D—H…A	d(D—H)/nm	d(H…A)/nm	d(D…A)/nm	∠DHA/(°)
C5—H5A…Cl1A	0.093	0.2795	0.3468	130
C2—H2A…Cl2	0.093	0.2699	0.3575	157
Cl3—H13A…Cl1	0.093	0.2757	0.3532	141
C14—H14B…Cl1	0.096	0.2808	0.3704	155

Fig.3 Molecular structure(A), coordination geometry of Cd1 ion(B), 1D chain structure(C) and supramolecular structure of complex 2(D)

Table 4 Selected bond distances(nm) and bond angles(°) of complexs 2*

Cd1—N1	0.2340(3)	Cd1—Cl1	0.2697(1)	Cd1—Cl2	0.2504(1)
Cd1—O1	0.2432(3)	Cd1—Cl1#1	0.2535(1)	Cd1—Cl2#2	0.2729(1)
N1—Cd1—O1	68.09(1)	Cl2—Cd1—Cl1#1	108.17(4)	N1—Cd1—Cl2#2	83.62(7)
N1—Cd1—Cl2	155.43(7)	N1—Cd1—Cl1	91.62(7)	O1—Cd1—Cl2#2	94.31(7)
O1—Cd1—Cl2	91.51(7)	O1—Cd1—Cl1	82.50(7)	Cl2—Cd1—Cl2#2	84.48(4)
N1—Cd1—Cl1#1	94.67(8)	Cl2—Cd1—Cl1	99.39(4)	Cl1#1—Cd1—Cl2#2	97.59(4)
O1—Cd1—Cl1#1	157.82(7)	Cl1#1—Cd1—Cl1	84.23(4)	Cl1—Cd1—Cl2#2	175.01(3)

Table 5 Hydrogen bond lengths and bond angles of complex 2

D—H…A	d(D—H)/nm	d(H…A)/nm	d(D…A)/nm	∠DHA/(°)
C7—H7A…Cl1A	0.096	0.2758	0.3494	134
C3—H3A…Cl1	0.093	0.2785	0.3570	142

Fig.4 UV-Vis spectra of complexes 1(A) and 2(B)

Fig.5 Normalized emission spectra of complex 1(A) and complex 2(B) in CH3OH, CH3CN, CH2Cl2 and in solid state

Fig.6 Decay curves of complex 1(A, C) and 2(B, D) in CH3OH, CH3CN, CH2Cl2(A, B) and in solid state(C, D) (A), (B): a. CH3OH; b. CH3CN; c. CH2Cl2.

Table 6 Photoluminescent data for complexes 1 and 2

Medium	Complex 1		Complex 2
Medium	Emission, λ_max/nm	Decay lifetime, τ/μs	Emission, λ_max/nm	Decay lifetime, τ/μs
CH₂Cl₂	390	38.10	400	23.83
CH₃CN	410	60.20	425	37.50
CH₃OH	420	38.10	433	19.83
Solid	440	20.20	473	19.08

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