2个新颖的(3,4,6)和(3,6)连接的多核金属有机骨架化合物的合成、 结构与性质

doi:10.7503/cjcu20160343

摘要/Abstract

摘要：

在水热和溶剂热条件下合成了2个新颖的金属有机骨架化合物{[Cu₃(BCPBA)₂(bpmp)(H₂O)]·2DMF}_n(1)和{Zn₃(BCPBA)₂(bip)(H₂O)₂}_n(2)[H₃BCPBA=3,5-双(4-羧基-苯氧基)苯甲酸; bpmp=1,4-二(吡啶-4-亚甲基)哌嗪; bip=1,3-二(咪唑基)丙烷]. 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2个化合物进行了表征. 结果表明, 化合物1属于单斜晶系, C2/m空间群, 是由羧酸连接3个二级结构单元[Cu₂(CO₂)₄]形成的具有自穿插结构的三维骨架结构, 其骨架拓扑符号为(4·8²)(8⁶)(4²·6⁸·8³·9·10); 化合物2属于三斜晶系, P $1 ˉ$ 空间群, 其骨架是由1个新颖的二级结构单元组成的拓扑结构为(4²·6)₂(4⁴·6²·8⁸·10)的三维超分子网络.

关键词: 金属有机骨架化合物, 自穿插, 3, 5-双(4-羧基-苯氧基)苯甲酸, 1, 4-二(吡啶-4-亚甲基)哌嗪, 1, 3-二(咪唑基)丙烷

Abstract:

Two novel polynuclcar metal-organic frameworks, namely, {[Cu₃(BCPBA)₂(bpmp)(H₂O)]·2DMF}_n(1) and {Zn₃(BCPBA)₂(bip)}_n(2)[H₃BCPBA=3,5-bi(4-carboxy-phenoxy)benzoic acid, bpmp=1,4-bis(pyridin-4-ylmethl)piperazine, bip=1,3-bis(imidazolyl)propane], were synthesized under solvothermal/hydrotherinal conditions. Their structures were determined by single-crystal X-ray diffraction(XRD) analysis and further characterized by infrared spectrosopy(IR), elemental analysis, and thermogravimetric analysis(TGA). Compound 1 is constructed by BCPBA^3- ligand linking three [Cu₂(CO₂)₄] clusters to form a 3D framework with (4·8²)(8⁶)(4²·6⁸·8³·9·10) topology. The 3D framework displays a self-penetra-ting phenomenon. Compound 2 exhibits a 3D framework with (4²·6)₂(4⁴·6²·8⁸·10) topology constructed by trinuclear Zn(Ⅱ) SBUs.

Key words: Metal-organic framework, Self-penetrating, 3, 5-Bi(4-carboxy-phenoxy)benzoic acid, 1, 4-Bis(pyridin-4-ylmethl)piperazine, 1, 3-Bis(imidazolyl)propane

中图分类号:

O614
O627.12

TrendMD:

赵仑, 赵长江. 2个新颖的(3,4,6)和(3,6)连接的多核金属有机骨架化合物的合成、结构与性质. 高等学校化学学报, 2016, 37(10): 1763.

ZHAO Lun, ZHAO Changjiang. Syntheses, Characterizations and Properties of Two Unusual (3,4,6) and (3,6)-Connected Polynuclear 3D Metal-organic Frameworks^†. Chem. J. Chinese Universities, 2016, 37(10): 1763.

图/表 7

Fig.1 Molecular structures of H3BCPBA(A), bpmp(B) and bip(C)

Table 1 Crystal data and structure refinement of compounds 1 and 2

Compound	1	2	Z	4	2
CCDC No.	1404000	1447781	D_c/(g·cm^-3)	0.737	1.678
Molecular formula	C₆₄H₅₆N₆O₁₉Cu₃	C₅₁H₃₄N₄O₁₈Zn₃	μ/mm^-1	0.595	1.605
Formula weight	1403.80	1187.06	F(000)	2564	1204
Crystal system	Monoclinic	Triclinic	Total/unique reflections	31840, 11316	17631, 11617
Space group	C2/m	P $1 ˉ$	R_int	0.0630	0.0220
a/nm	2.1738(2)	0.98622(6)	Observed reflections[I>2σ(I)]	6298	8729
b/nm	3.8788(4)	1.01973(7)	N_ref, N_par	11316, 373	11617, 685
c/nm	1.57057(14)	2.60962(17)	R₁, wR₂[I>2σ(I)]	0.0478, 0.1341	0.0403, 0.0987
α/(°)	90.00	92.9990(10)	R₁, wR₂(all data)	0.0859,0.1427	0.0630,0.1162
β/(°)	121.086(2)	99.3410(10)	S	0.921	1.056
γ/(°)	90.00	113.8340(10)	Largest diff. peak and hole/(e·nm^-3)	630, -348	752, -655
V/nm³	11.3406(18)	2.3485(3)

Table 1 Crystal data and structure refinement of compounds 1 and 2

Compound	1	2	Z	4	2
CCDC No.	1404000	1447781	D_c/(g·cm^-3)	0.737	1.678
Molecular formula	C₆₄H₅₆N₆O₁₉Cu₃	C₅₁H₃₄N₄O₁₈Zn₃	μ/mm^-1	0.595	1.605
Formula weight	1403.80	1187.06	F(000)	2564	1204
Crystal system	Monoclinic	Triclinic	Total/unique reflections	31840, 11316	17631, 11617
Space group	C2/m	P $1 ˉ$	R_int	0.0630	0.0220
a/nm	2.1738(2)	0.98622(6)	Observed reflections[I>2σ(I)]	6298	8729
b/nm	3.8788(4)	1.01973(7)	N_ref, N_par	11316, 373	11617, 685
c/nm	1.57057(14)	2.60962(17)	R₁, wR₂[I>2σ(I)]	0.0478, 0.1341	0.0403, 0.0987
α/(°)	90.00	92.9990(10)	R₁, wR₂(all data)	0.0859,0.1427	0.0630,0.1162
β/(°)	121.086(2)	99.3410(10)	S	0.921	1.056
γ/(°)	90.00	113.8340(10)	Largest diff. peak and hole/(e·nm^-3)	630, -348	752, -655
V/nm³	11.3406(18)	2.3485(3)

Fig.2 Coordination environment of the Cu(Ⅱ) ions(A), a 3D framework formed by each BCPBA3- ligand linking three secondary building units(B), an infinite 3D framework generated by the linkage of the adjacent dinuclear Cu2 SBUs by bpmp ligand(C) and view of 3D self-penetrating structure(D, E)Hydrogen atoms are omitted for clarity. Symmetry codes: #1: -x, y, -z; #2: -x, -y+1, -z; #3: x, -y+1, z; #4: -x+0.5, -y+0.5, -z; #5: -x+0.5, -y+0.5, -z-1; #6: x, y, z-1; #7: x, y, z+1; #8: -x-0.5, -y+0.5, -z-2.

Fig.3 Coordination environment of the Zn(Ⅱ) ions(A), the trinuclear Zn(Ⅱ) SBUs(B) and the 3D framework with (42·6)2(44·62·88·10) topology structure(C)Hydrogen atoms are omitted for clarity. Symmetry codes: #1: -x+1, -y, -z+1; #2: -x+1,-y,-z+2; #3: -x, -y, -z+1; #4: -x+2, -y+1, -z+2.

Fig.4 Experimental(a) and simulated(b) PXRD patterns of compound 1(A) and compound 2(B)

Fig.5 TG curves of compounds 1(a) and 2(b)

Fig.6 Solid-state emission spectra of compound 2(a), H3BCPBA(b) and bip(c) at room temperature

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