具有螺旋结构的金属镍有机-无机配位聚合物的合成及表征

doi:10.7503/cjcu20150903

摘要/Abstract

摘要：

在水热体系中合成了3个中心金属为镍离子, 以六配位扭曲八面体构型形成的具有螺旋结构的配位聚合物{[Ni₂L₂(bib)₂·2H₂O]·5H₂O}_n(1), [Ni₂L₂(bpy)]_n(2)和{[Ni₂L₂(bibpip)₂·2H₂O]·6H₂O}_n(3)[H₂L=4,4'-三苯胺二甲酸; bib=1,3-二(咪唑基)苯; bpy=4,4-联吡啶; bibpip=1,4-二(4-咪唑苄基)哌嗪]. 通过单晶及粉末X射线衍射、红外光谱、元素分析和热重分析对这3种化合物进行了表征. 结果表明, 化合物1属于单斜晶系, C2/c空间群, 其骨架为具有{4²·6⁵·8}拓扑结构的二维层结构; 化合物2属于斜方晶系, Fdd2空间群, 其骨架为具有{4⁸·5⁴·6³}拓扑结构的三维超分子网络; 化合物3属于三斜晶系, P $1 ˉ$ 空间群, 为1个五重穿插的三维超分子网络, 其骨架具有{4⁴·6²}拓扑结构.

关键词: 4, 4'-三苯胺二甲酸, 1, 3-二(咪唑基)苯, 4, 4-联吡啶, 1, 4-二(4-咪唑苄基)哌嗪, 金属有机骨架化合物

Abstract:

The multidenate 4,4'-(phenylazanediyl)dibenzoic acid(H₂L) ligand and nickel(Ⅱ) ions reacted with 1,3-bis(imidazol-l-yl)benzene(bib) or 4,4-bipyridine or 1,4-bis[4-(1H-imidazol-l-yl)benzyl]piperazine(bibpip) under the solvothermal reactions, three new metal-organic frameworks with helical structure, namely{[Ni₂L₂(bib)₂·2H₂O]·5H₂O}_n(1), [Ni(HL)₂(bpy)]_n(2) and {[Ni₂L₂(bibpip)₂·2H₂O]·6H₂O}_n(3), were presented along with an analysis of the structural features by single-crystal X-ray diffraction. Complexes 1—3 were also characterized by FTIR spectroscopy, elemental analyses, thermal analysis and power X-ray diffraction(PXRD). The results showed that the complex 1 crystallizes in the monoclinic space group C2/c, exhibited two-dimensional(2D) layer with {4²·6⁵·8} topology structure; complex 2 crystallizes in the orthorhombic space group Fdd2, gave a 3D framework with {4⁸·5⁴·6³} topology structure; complex 3 exhibits a 5-fold interpenetrating 3D framework with a {4⁴·6²} topology.

Key words: 4, 4'-(Phenylazanediyl)dibenzoic acid, 1, 3-Bis(imidazol-l-yl)benzene, 4, 4-Bipyridine, 1, 4-Bis[4-(1H-imidazol-l-yl)benzyl]piperazine, Metal-organic framework

中图分类号:

TrendMD:

赵仑, 白鹤龙, 孙二军, 王晓峰, 王子忱. 具有螺旋结构的金属镍有机-无机配位聚合物的合成及表征. 高等学校化学学报, 2016, 37(7): 1250.

ZHAO Lun, BAI Helong, SUN Erjun, WANG Xiaofeng, WANG Zichen. Synthesis and Characterization of Novel Ni(Ⅱ) Metal-organic Frameworks with Helical Crystal Structure^†. Chem. J. Chinese Universities, 2016, 37(7): 1250.

图/表 7

Scheme 1 molecular structures of ligands and synthetic routes of coordination complexes

Table 1 Crystal data and structure refinement of complexes 1—3

Complex	1	2	3
CCDC No.	1435639	1435783	1435640
Molecular formula	C₆₄H₆₀Ni₂N₁₀O₁₅	C₅₀H₃₆NiN₄O₈	C₈₈ $H 9 4$ Ni₂N₁₄O₁₆
Formula weight	1322.61	879.54	1721.16
Crystal system	Monoclinic	Orthorhombic	Triclinic
Space group	C2/c	Fdd2	P $1 ˉ$
a/nm	2.2743(6)	1.47100(15)	1.1534(2)
b/nm	1.8062(5)	4.9840(5)	1.3067(2)
c/nm	1.8868(8)	1.12261(11)	1.4839(3)
α/(°)	90.00	90.00	104.106(4)
β/(°)	123.155(4)	90.00	103.021(4)
γ/(°)	90.00	90.00	91.669(4)
V/nm³	6.489(4)	8.2303(14)	2.1047(7)
Z	4	8	2
D_c/(Mg·m^-3)	1.354	1.416	1.355
F(000)	2744	3632	900
GOF on F²	0.929	1.047	0.941
R₁/wR₂[I>2σ(I)]	0.0713/0.1886	0.0639/0.1599	0.0909/0.2177
R₁/wR₂(all data)	0.1385/0.2230	0.0934/0.1815	0.1972/0.2648

Table 1 Crystal data and structure refinement of complexes 1—3

Complex	1	2	3
CCDC No.	1435639	1435783	1435640
Molecular formula	C₆₄H₆₀Ni₂N₁₀O₁₅	C₅₀H₃₆NiN₄O₈	C₈₈ $H 9 4$ Ni₂N₁₄O₁₆
Formula weight	1322.61	879.54	1721.16
Crystal system	Monoclinic	Orthorhombic	Triclinic
Space group	C2/c	Fdd2	P $1 ˉ$
a/nm	2.2743(6)	1.47100(15)	1.1534(2)
b/nm	1.8062(5)	4.9840(5)	1.3067(2)
c/nm	1.8868(8)	1.12261(11)	1.4839(3)
α/(°)	90.00	90.00	104.106(4)
β/(°)	123.155(4)	90.00	103.021(4)
γ/(°)	90.00	90.00	91.669(4)
V/nm³	6.489(4)	8.2303(14)	2.1047(7)
Z	4	8	2
D_c/(Mg·m^-3)	1.354	1.416	1.355
F(000)	2744	3632	900
GOF on F²	0.929	1.047	0.941
R₁/wR₂[I>2σ(I)]	0.0713/0.1886	0.0639/0.1599	0.0909/0.2177
R₁/wR₂(all data)	0.1385/0.2230	0.0934/0.1815	0.1972/0.2648

Fig.1 Coordination environment of the Ni(Ⅱ) ions(A), view of 2D sheets(B), the {42·63·8} topology net(C), 3D framework(D), the helical chains(E) and the opposite handedness in the A and B layers(F, G) The hydrogen atoms are omitted for clarity. Symmetry codes: #1: x-0.5, y-0.5, z; #2: -x+1.5, y-0.5, -z-0.5; #3: -x+1.5, y+0.5, -z-0.5; #4: x+0.5, y+0.5, z.

Fig.2 Coordination environment of the Ni(Ⅱ) ions(A), view of 3D framework(B, C), {48·54·63} topology net(D) and view of the helical chains(E) The hydrogen atoms are omitted for clarity.Symmetry codes: #1: -x+1.25, y+0.25, z+0.25; #2: -x+1.5, -y+0.5, z; #3: x, y, z+1; #4: x, y, z-1; #5: -x+1.25, y-0.25, z-0.25.

Fig.3 Coordination environment of the Ni(Ⅱ) ions(A), view of 2D wave-like sheets(B) and {44·62} topology net(C), schematic view of the 5-fold interpenetrating framework(D) and view of the helical chains(E) The hydrogen atoms are omitted for clarity. Symmetry codes: #1: x, y, z-1; #2: -x+2, -y-1, -z+2; #3: -x-1, -y, -z+1; #4: x, y, z+1.

Fig.4 Experimental(a) and simulated(b) PXRD patterns of complexes 1(A), 2(B) and 3(C)

Fig.5 TG curves of complexes 1—3(a—c)

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