由芳香羧酸构筑的系列Ni(Ⅱ)配合物的合成、 结构及光电性能

doi:10.7503/cjcu20180076

摘要/Abstract

摘要：

采用水热法设计合成了6个基于芳香羧酸的Ni(Ⅱ)配合物: [Ni(pz)₄(H₂O)₂]·2H₂btc·H₂O(1), {[Ni₂(pz)₈(btec)]·4H₂O}_n(2), {[Ni(H₂btec)(phen)]∙2H₂O}_n(3), [Ni(Hbdc)₂(pz)₄](4), {[Ni₃(bdc)₃(pz)₁₂]·2H₂O}_n(5)和[Ni(bdc)(pz)₂(H₂O)]_n(6)(pz=吡唑, H₃btc=1,3,5-苯三甲酸, H₄btec=1,2,4,5-苯四甲酸, phen=1,10-邻菲罗啉, H₂bdc=邻苯二甲酸). 通过单晶X射线衍射、红外光谱(IR)、紫外-可见-近红外吸收光谱、元素分析、粉末X射线衍射(XRD)和表面光电压光谱(SPS)对其进行了结构和性质表征. 6个配合物的金属Ni(Ⅱ)中心呈五或六配位. 配合物1和4具有完全由氢键网联成的2D超分子结构; 配合物2和3是通过采取单齿/桥双齿配位模式的btec^4-构筑的2D配位骨架结构; 配合物5和6是由采取单齿/螯合双齿配位模式的bdc^2-构筑的1D配位骨架结构, 并由氢键连接成2D结构. 6个配合物在紫外和可见光诱导下均呈现出一定的光-电转换性能. 当对配合物施加外加电场时, 6个配合物的光电响应因配合物组成、结构键连方式以及配体种类的不同而呈现规律性变化.

关键词: 芳香羧酸, Ni(Ⅱ)配合物;, 晶体结构, 光物理性质, 光电性能

Abstract:

Six Ni(Ⅱ) complexes based on aromatic carboxylic ligands, [Ni(pz)₄(H₂O)₂]·2H₂btc·H₂O(1), {[Ni₂(pz)₈(btec)]·4H₂O}_n(2), {[Ni(H₂btec)(phen)]∙2H₂O}_n(3), [Ni(Hbdc)₂(pz)₄](4), {[Ni₃(bdc)(pz)₁₂]·2H₂O}_n(5) and [Ni(bdc)(pz)₂(H₂O)]_n(6)(pz=pyrazole, H₃btc=1,3,5-benzenetricarbolylic acid, H₄btec=1,2,4,5-benzenetetracarboxylic acid, phen=1,10-phennanthroline, H₂bdc=1,2-benzenedicarboxylic acid), were hydrothermally synthesized. All the complexes were structurally and photophysically characterized by means of single crystal X-ray diffraction, infrared(IR) and UV-Vis-NIR electronic spectra, elemental analysis, X-ray diffraction(XRD) and surface photovoltage spectra(SPS). The Ni(Ⅱ) centers in six complexes have the square-pyramid or octahedral coordination environment. Complexes 1 and 4 have 2D supramolecular structure networked by hydrogen bonds. Complexes 2 and 3 possess 2D coordination framework structure constructed by btec^4- ligands with monodentate and monoatomic bridging modes. Complexes 5 and 6 have 1D coordination chain structure built by bdc^2-anions with monodentate/chelating coordination modes, which are further networked into 2D supramolecules by hydrogen bonds. All the six complexes exhibit certain photo-electric conversion properties under the inducement of UV-Vis lights. When a positive electric field is applied to the six complexes, the intensity change of photoelectric response of the six complexes presents difference which correlates with the bonding mode of the structure and type of the organic ligands.

Key words: Aromatic carboxylic acid, Ni(Ⅱ) complex;, Crystal structure, Photophysical property, Photoelectric property

中图分类号:

O614

TrendMD:

贠吉星, 胡志莉, 李禹蒙, 金晶, 陈冲, 鄢欣, 刘永华, 丁榆, 迟玉贤, 牛淑云. 由芳香羧酸构筑的系列Ni(Ⅱ)配合物的合成、结构及光电性能. 高等学校化学学报, 2018, 39(10): 2161.

YUN Jixing,HU Zhili,LI Yumeng,JIN Jing,CHEN Chong,YAN Xin,LIU Yonghua,DING Yu,CHI Yuxian,NIU Shuyun. Synthesis, Structure and Photoelectric Property of A Series of Ni(Ⅱ) Complexes Constructed Through Aromatic Carboxylic Ligands^†. Chem. J. Chinese Universities, 2018, 39(10): 2161.

图/表 10

Table 1 Crystallographic parameters of complexes 1-6

Complex	1	2	3	4	5	6
Formula	C₃₀H₃₂NiN₈O₁₅	C₃₄H₄₂N₁₆Ni₂O₁₂	C₂₂H₁₆N₂NiO₁₀	C₂₈H₂₆N₈NiO₈	C₆₀H₅₂N₂₄Ni₃O₁₄	C₁₄H₁₄N₄NiO₅
Formula weight	803.35	984.26	527.08	661.28	1509.39	377.00
Crystal system Space group	Monoclinic P2₁/n	Triclinic P $1 ˉ$	Triclinic P $1 ˉ$	Monoclinic P2₁/c	Monoclinic C2/c	Monoclinic C2/c
a/nm	1.5085(5)	0.8855(2)	0.9535(2)	1.0086(1)	3.0761(2)	2.2177(6)
b/nm	1.4561(5)	1.1175(2)	1.0668(2)	1.5752(2)	1.2120(1)	0.7992(2)
c/nm	1.6750(6)	1.1446(2)	1.0925(2)	0.9643(2)	1.8510(2)	1.7678(4)
α/(°)	90	82.871(2)	76.905(3)	90	90	90
β/(°)	112.201(5)	74.036(2)	74.780(4)	100.205(2)	93.300(2)	103.685(4)
γ/(°)	90	74.150(2)	74.759(3)	90	90	90
V/nm³	3.406(2)	1.0460(3)	1.0197(4)	1.5077(3)	6.8893(8)	3.0443(13)
Z	4	1	2	2	4	8
D_c/(g·cm^-3)	1.566	1.562	1.717	1.457	1.455	1.645
μ/mm^-1	0.655	0.981	1.019	0.706	0.892	1.309
F(000)	1664	510	540	684	3104	1552
Reflections collected Unique(R_int)	14148 5286(0.0585)	5435 4003(0.0138)	5350 3919(0.0268)	8046 2957(0.0254)	20873 8237(0.0224)	7657 2982(0.0703)
GOOF	1.062	1.067	1.021	1.101	1.044	0.969
R₁, wR₂[I>2σ(I)]	0.0700, 0.1781	0.0439, 0.1275	0.0519, 0.1130	0.0499, 0.1581	0.0444,0.1394	0.0508,0.1002
R₁, wR₂(all data)	0.1102, 0.2082	0.0507, 0.1338	0.0947, 0.1271	0.0560, 0.1626	0.0618, 0.1512	0.1003,0.1120
CCDC No.	1818300	1818309	1818310	1818311	1818312	1818313

Table 1 Crystallographic parameters of complexes 1-6

Complex	1	2	3	4	5	6
Formula	C₃₀H₃₂NiN₈O₁₅	C₃₄H₄₂N₁₆Ni₂O₁₂	C₂₂H₁₆N₂NiO₁₀	C₂₈H₂₆N₈NiO₈	C₆₀H₅₂N₂₄Ni₃O₁₄	C₁₄H₁₄N₄NiO₅
Formula weight	803.35	984.26	527.08	661.28	1509.39	377.00
Crystal system Space group	Monoclinic P2₁/n	Triclinic P $1 ˉ$	Triclinic P $1 ˉ$	Monoclinic P2₁/c	Monoclinic C2/c	Monoclinic C2/c
a/nm	1.5085(5)	0.8855(2)	0.9535(2)	1.0086(1)	3.0761(2)	2.2177(6)
b/nm	1.4561(5)	1.1175(2)	1.0668(2)	1.5752(2)	1.2120(1)	0.7992(2)
c/nm	1.6750(6)	1.1446(2)	1.0925(2)	0.9643(2)	1.8510(2)	1.7678(4)
α/(°)	90	82.871(2)	76.905(3)	90	90	90
β/(°)	112.201(5)	74.036(2)	74.780(4)	100.205(2)	93.300(2)	103.685(4)
γ/(°)	90	74.150(2)	74.759(3)	90	90	90
V/nm³	3.406(2)	1.0460(3)	1.0197(4)	1.5077(3)	6.8893(8)	3.0443(13)
Z	4	1	2	2	4	8
D_c/(g·cm^-3)	1.566	1.562	1.717	1.457	1.455	1.645
μ/mm^-1	0.655	0.981	1.019	0.706	0.892	1.309
F(000)	1664	510	540	684	3104	1552
Reflections collected Unique(R_int)	14148 5286(0.0585)	5435 4003(0.0138)	5350 3919(0.0268)	8046 2957(0.0254)	20873 8237(0.0224)	7657 2982(0.0703)
GOOF	1.062	1.067	1.021	1.101	1.044	0.969
R₁, wR₂[I>2σ(I)]	0.0700, 0.1781	0.0439, 0.1275	0.0519, 0.1130	0.0499, 0.1581	0.0444,0.1394	0.0508,0.1002
R₁, wR₂(all data)	0.1102, 0.2082	0.0507, 0.1338	0.0947, 0.1271	0.0560, 0.1626	0.0618, 0.1512	0.1003,0.1120
CCDC No.	1818300	1818309	1818310	1818311	1818312	1818313

Fig.1 2D Anion layer(A) and H-bonding interaction between anion and cation(B) of complex 1

Fig.2 2D coordination layer on the bc plane of complex 2

Fig.3 2D coordination layer(A) and the H-bonding 3D supramolecular structure(B) of coordination polymer 3Phen molecules are omitted for clarity.

Fig.4 2D H-bonding layer on the bc plane of complex 4

Fig.5 1D chain(A) and 2D H-bonding layer on the ac plane(B) of complex 5

Fig.6 H-bonded 2D layer on the bc plane of complex 6

Fig.7 UV-Vis-NIR absorption spectra of complexes 1—6(A) a. Complex 1; b. complex 2; c. complex 4; d. complex 5; e. complex 6. (B) Complex 3.

Fig.8 FISPS of complexes 1—6(A—F) under different applied electric field

Fig.9 Experimental(a1—a6) and simulated(b1—b6) XRD patterns of complexes 1—6

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