混合配体构筑的Zn(Ⅱ)金属有机骨架化合物的合成、 结构与荧光性质

doi:10.7503/cjcu20150301

摘要/Abstract

摘要：

在水热条件下, 利用锌离子与2种有机配体合成出1个结构新颖的金属有机骨架化合物[Zn₂(BPDC)(IN)₂](H₂BPDC=4,4'-联苯二羧酸; HIN=异烟酸), 并通过单晶X射线衍射、红外光谱、热重分析和荧光光谱等对该化合物进行了表征. 结果表明, 该化合物结构中Zn离子与BPDC的羧基形成双核金属次级结构单元[Zn₂(—CO₂)₂(IN)₂], 相邻次级结构单元通过IN配离子连接形成[Zn₂(—CO₂)₂(IN)₂]_∞二维层面, 相邻的二维层通过BPDC相互连接形成具有三重互穿的简单格子拓扑结构. 该化合物表现出良好的荧光性质.

关键词: 水热合成, 金属有机骨架, 混合配体, 互穿结构

Abstract:

A new metal-organic framework compound, [Zn₂(BPDC)(IN)₂](H₂BPDC=biphenyl-4,4'-dicarboxylic acid, HIN=isonicotinic acid), was synthesized by self-assembly of mixed ligands and Zn(Ⅱ) under hydrothermal conditions and characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, thermogravimetric analysis and fluorescence spectra. Single-crystal X-ray diffraction analysis revealed that Zn ions connected to carboxyl of BPDC, forming dual-core metal secondary building units(SBUs) [Zn₂(—CO₂)₂(IN)₂], the SBUs connected to the adjacent SBUs through IN to form an unlimited extension two-dimensional network [Zn₂(—CO₂)₂(IN)₂]_∞. The adjacent [Zn₂(—CO₂)₂(IN)₂]_∞ layers were interconnected by BPDC ligand to form a simple three-dimensional framework. The three-dimensional framework of the compound has simple cubic lattice topology of threefold interpenetrating. In addition, luminescence properties of [Zn₂(BPDC)(IN)₂] in the solid state were characterized.

Key words: Hydrothermal synthesis, Metal-organic framework, Mixed ligand, Interpenetrated structure

中图分类号:

O614

TrendMD:

黄楚婷, 吴小峰, 李光华, 高路, 冯守华. 混合配体构筑的Zn(Ⅱ)金属有机骨架化合物的合成、结构与荧光性质. 高等学校化学学报, 2015, 36(9): 1661.

HUANG Chuting, WU Xiaofeng, LI Guanghua, GAO Lu, FENG Shouhua. Synthesis, Structure and Luminescence Propreties of 3D Interpenetrating Metal-organic Frameworks Built by Zn(Ⅱ) and Mixed Ligands^†. Chem. J. Chinese Universities, 2015, 36(9): 1661.

图/表 8

Table 1 Crystal data and structure refinement for Zn2(BPDC)(IN)2

Empirical formula	C₂₆H₁₆N₂O₈Zn₂	Z	2
Formula weight	615.15	D_c/(Mg·m^-3)	1.688
T/K	293(2)	F(000)	620
Crystal system	Monoclinic	R_int	0.0699
Space group	P2₁/c	Goodness-of-fit on F²	1.106
a/nm	0.64963(13)	Final R indices[I>2σ(I)]	R₁=0.0518
b/nm	1.7952(4)		wR₂=0.1214
c/nm	1.1054(2)	R indices(all data)	R₁=0.0760
β/(°)	110.13(3)		wR₂=0.1408
V/nm³	1.2103(4)	Largest diff. peak and hole/(e·nm^-3)	820 , -927

Fig.1 Structures of the rigid dipyridyl bridging ligand 3,6-di(pyridin-4-yl)-1,2,4,5-tetra-zine(A) and aromatic dicarboxylate ligand biphenyl-4,4'-dicarboxylic acid(B)

Fig.2 Coordination environment of Zn2+ in [Zn2(BPDC)(IN)2]

Fig.3 Views of the infinite two-dimensional layer constructed from dinuclear Zn2+ coordinated to IN ligands with the quadrangular channels of 1.205 nm×1.022 nm(A), the three-dimensional framework of [Zn2(BPDC)(IN)2] formed by [Zn2(—CO2)2(IN)2]∞ and BPDC ligands(B)and two-dimensional network of [Zn2(BPDC)(IN)2] with the quadrangular channels of 1.125 nm×1.462 nm(C)

Fig.4 Schematic view of the threefold interpenetrating three-dimensional networks in [Zn2(BPDC)(IN)2]

Fig.5 XRD patterns for [Zn2(BPDC)(IN)2]a. Experimental; b. simulated.

Fig.6 TG curve of [Zn2(BPDC)(IN)2]

Fig.7 Solid state excitation(a) and emission spectra(b) of [Zn2(BPDC)(IN)2]

参考文献 31

[1]	Wang X. Y., Wang L., Wang Z. M., Gao S., J. Am. Chem. Soc., 2006, 128, 674—675
[2]	Sun T., Ying J. Y., Nature, 1997, 389, 704—706
[3]	Baur W. H., Nature Materrials, 2003, 2, 17—18
[4]	Wirnsberger G., Yang P., Scott B.J., Chmelka B. F., Stucky G. D., Spectro-chim. Acta A, 2001, 57, 2049—2060
[5]	Mathiowitz E., Jacob J. S., Jong Y. S., Carino G. P., Chickering D. E., Chaturved P., Santos C. A., Vijayaraghavan K., Montgomery S., Bassett M., Morrell C., Nature, 1997, 386, 410—414
[6]	Wigley T. M. L., Richels R., Edmonds J. A., Nature, 1996, 379, 240—243
[7]	Janiak C.,Dalton Trans., 2003, 2781—2804
[8]	Collins D. J., Zhou H. C., J. Mater. Chem., 2007, 17, 3154—3160
[9]	Li Z. Q., Wang A., Guo C. Y., Hu W. N., Tai Y. F., Chem. J. Chinese Universities, 2013, 34(11), 2470—2477
	(李宗群, 汪艾, 郭春燕, 胡文娜, 邰艳芳. 高等学校化学学报, 2013, 34(11), 2470—2477)
[10]	Zhang Y., Yang X. G., Wang Q. Y., Yao J., Hu J., Wang G. Y., Chem. J. Chinese Universities, 2014, 35(3), 613—618
	(张毅, 杨先贵, 王庆印, 姚洁, 胡静, 王公应. 高等学校化学学报, 2014, 35(3), 613—618)
[11]	Subramanian S., Zaworotk M. J., Angew. Chem. Int. Ed. Engl., 1995, 34(19), 2127—2129
[12]	Yaghi O. M., Li H. L., Groy T. L. Inorg. Chem., 1997, 36, 4292—4293
[13]	Yaghi O. M., O’Keeffe M., Ockwig N. W., Chse H. K., Eddaoudi M., Kim J., Nature, 2003, 423, 705—714
[14]	Xue M., Chen S. R., Guo L. J., Qiu S. L., Chem. J. Chinese Universities, 2012, 33(9), 1889—1894
	(薛铭, 陈思如, 郭莉佳, 裘式纶. 高等学校化学学报, 2012, 33(9), 1889—1894)
[15]	Hu B., Feng M. L., Li J. R., Lin Q. P., Huang X. Y., Angew. Chem. Int. Ed., 2011, 50, 8110—8113
[16]	Zheng S. T., Wu T., Chou C., Fuhr A., Feng P. Y., Bu X. H., J. Am. Chem. Soc., 2012, 134, 4517—4520
[17]	Pramanik S., Zheng C., Zhang X., Emge T. J., Li J., J. Am. Chem. Soc., 2011, 133, 4153—4155
[18]	Takashima Y., Martínez V.M., Furukawa S., Kondo M., Shimomura S., Uehara H., Nakahama M., Sugimoto K., Kitagawa S., Nature Commun., 2010, 1—8
[19]	Dinolfo P. H., Williams M. E., Stern C. L., Hupp J. T., J. Am. Chem. Soc., 2004, 126, 12989—13001
[20]	Hsu C. J., Tang S. W., Wang J. S., Wang W. J., Mol. Cryst. Liq. Cryst., 2006, 456, 201—208
[21]	Hao Z. M., Fang R. Q., Wu H. S., Zhang X. M., Inorg. Chem., 2008, 48(18), 8197—8203
[22]	Zhang X. M., Fang R. Q., Wu H. S., J. Am. Chem. Soc., 2005, 127, 7670—7671
[23]	He Y. K., Han Z. B., Ma Y., Zhang X. D., Inorg. Chem. Commun., 2007, 10, 829—832
[24]	Zhu H. B., Ji J. F., Zhang Y. W., Gou S. H., Inorg. Chem. Commun., 2009, 12, 240—242
[25]	Zeng M.H., Feng X. L., Zhang W. X., Chen X. M.,Dalton Trans., 2006, 5294—5303
[26]	Evans O. R., Lin W., Cryst. Growth Des., 2001, 1, 9—11
[27]	Li J., Peng Y., Liang H.W., Yu Y., Xin B. J., Li G. H., Shi Z., Feng S. H.,Eur. J. Inorg. Chem., 2011, 2712—2719
[28]	Qin J. H., Ma L. F., Hu Y., Wang L. Y., Cryst. Eng. Comm., 2012, 14, 2891—2898
[29]	Feng W. J., Xu Y., Zhou G. P., Zhang C. L., Zheng X. F., Inorg. Chem. Commun., 2007, 10, 49—52
[30]	Yuan Q., Liu B., Bull. Korean Chem. Soc., 2006, 27, 150—152
[31]	Liu B., Xu L., Guo G.C.,J. Solid State Chem., 2006, 883—890