Synthesis, Structure and Luminescence Propreties of 3D Interpenetrating Metal-organic Frameworks Built by Zn(Ⅱ) and Mixed Ligands†

doi:10.7503/cjcu20150301

Abstract

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

CLC Number:

O614

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2015, 36(9): 1661.

Figures/Tables 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]

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