新型氯桥连一维链结构Cd(Ⅱ)配位聚合物的合成、 结构及蓝光性能

doi:10.7503/cjcu20140986

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (3): 411.doi: 10.7503/cjcu20140986

• 研究论文: 无机化学 • 上一篇下一篇

新型氯桥连一维链结构Cd(Ⅱ)配位聚合物的合成、结构及蓝光性能

黄尖¹, 刘志刚¹, 范瑞清¹(), 董玉伟¹, 张会杰¹, 王雨雷², 杨玉林¹()

1. 哈尔滨工业大学化学系
2. 航天学院可调谐激光国防科技重点实验室, 哈尔滨 150001

收稿日期:2014-11-17 出版日期:2015-03-10 发布日期:2015-02-04
作者简介:联系人简介: 范瑞清, 女, 博士, 教授, 博士生导师, 主要从事功能配合物研究. E-mail: fanruiqing@hit.edu.cn. 杨玉林, 男, 博士, 教授, 博士生导师, 主要从事光电功能材料研究. E-mail: ylyang@hit.edu.cn
基金资助:
国家自然科学基金(批准号: 21171044, 21371040)、国家重点基础研究发展计划项目(批准号: 2013CB632900)、哈尔滨工业大学理学创新研究发展培育计划项目(批准号: A201416, B201414)和理工医交叉学科基础研究培育计划项目(批准号: HIT.IBRSEMA.201409)资助

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

HUANG Jian¹, LIU Zhigang¹, FAN Ruiqing^1,^*(), DONG Yuwei¹, ZHANG Huijie¹, WANG Yulei², YANG Yulin^1,^*()

1. Department of Chemistry
2. National Key Laboratory of Science and Technology on Tunable Laser,School of Astraunutics, Harbin Institute of Technology, Harbin 150001, China

Received:2014-11-17 Online:2015-03-10 Published:2015-02-04
Contact: FAN Ruiqing,YANG Yulin E-mail:fanruiqing@hit.edu.cn;ylyang@hit.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21171044, 21371040), the National Key Basic Research Program of China(No.2013CB632900), the Program for Innovation Research of Science in Harbin Institute of Technology, China(Nos.A201416, B201414) and the Fundamental Research Funds for the Central Universities of China(No.201409)

摘要/Abstract

摘要：

利用2-乙酰基吡啶(acpy) 和2-邻甲基苯胺在甲醇中回流反应得到新型希夫碱配体2-{1-[(2-甲基苯基) 亚氨基]-乙基}吡啶)(mpep) , 通过溶剂热法将acpy和mpep与氯化镉反应得到2种新型氯桥连一维之字链结构Cd(Ⅱ) 配位聚合物{[Cd(mpep) ]Cl₂}_n(配合物1)和{[Cd(acpy) ]Cl₂}_n(配合物2). 利用单晶X射线衍射、核磁共振氢谱、元素分析和红外光谱对配合物1和配合物2进行结构表征. 结果表明, 配合物1和配合物2均为一维之字链状结构. 在配合物1中, Cd与mpep配体中2个氮原子和4个氯原子配位, 呈六配位顺式八面体构型, 并通过2个Cl原子桥连形成一维之字链状结构. 在配合物2中, 中心金属Cd(Ⅱ) 与acpy中的氮原子、氧原子和4个氯原子配位, 也呈六配位顺式八面体构型, 进一步通过Cl原子桥连相邻金属形成一维之字链状结构. 在3种不同极性的溶剂(CH₃OH, CH₃CN和 CH₂Cl₂)中, 两种配位聚合物均呈现蓝色荧光(390~433 nm) , 说明2种配位聚合物具有弱溶剂效应; 在固态室温下两种配位聚合物也呈现蓝色荧光, 最大发射波长分别为440和473 nm. 固态最大发射波长比溶液中红移的原因是分子中存在氢键, 降低了基态与激发态之间的能级差. 在室温下, 配合物1和配合物2在3种溶液和固态中均显示出较长的荧光寿命(19.08~60.20 μs) .

关键词: Cd(Ⅱ) 配合物, 希夫碱, 蓝光性能, 荧光寿命

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

中图分类号:

O613

TrendMD:

黄尖, 刘志刚, 范瑞清, 董玉伟, 张会杰, 王雨雷, 杨玉林. 新型氯桥连一维链结构Cd(Ⅱ)配位聚合物的合成、结构及蓝光性能. 高等学校化学学报, 2015, 36(3): 411.

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^†. Chem. J. Chinese Universities, 2015, 36(3): 411.

图/表 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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新型氯桥连一维链结构Cd(Ⅱ)配位聚合物的合成、结构及蓝光性能

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

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新型氯桥连一维链结构Cd(Ⅱ)配位聚合物的合成、 结构及蓝光性能

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

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新型氯桥连一维链结构Cd(Ⅱ)配位聚合物的合成、结构及蓝光性能

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