LSRT #841206, VOL 0, ISS 0
A 63-Nets Framework Constructed by Cadmium(II) Hexafluorosilicate and 3-(Pyridin-4-yl)benzenamine: Synthesis, Structure, and Luminescence Property DE-QIANG QI, GUI-GE HOU, XUE-JIE WANG, YI-PING ZHANG, AND JIN-ZONG YOU
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry (2015) 0, 1–4 Copyright © Taylor & Francis Group, LLC ISSN: 1553-3174 print / 1553-3182 online DOI: 10.1080/15533174.2013.841206
A 63-Nets Framework Constructed by Cadmium(II) Hexafluorosilicate and 3-(Pyridin-4-yl)benzenamine: Synthesis, Structure, and Luminescence Property DE-QIANG QI1, GUI-GE HOU2, XUE-JIE WANG1, YI-PING ZHANG1, and JIN-ZONG YOU1
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School of Science and Technology, Zhejiang International Studies University, Hangzhou, Zhejiang, P. R. China School of Pharmacy, Binzhou Medical University, Yantai, Shandong, P. R. China
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Received 6 June 2013; accepted 1 September 2013
A novel 63-nets framework {[Cd(SiF6)(C11H10N2)2]¢(CH2Cl2)¢(H2O)}n (1) was generated based on asymmetric ligand 3-(pyridin-4-yl) benzenamine (L). L acts as a bidentate ligand to link Cd(II) centers into a 63-nets topology with rectangular channels encapsulating dichloromethane and water as guest molecules. In addition, their luminescent properties were investigated primarily in the solid 10 state, which is basically related to its incorporation into the metal-containing complexes. The result displays that the choice of the amino-functionalized pyridine-containing ligand leading to special connection patterns and diversity of the hydrogen bonds plays a crucial role in the construction of the novel topological framework with interesting luminescent property. Keywords: metal-organic framework, structure, 63-nets, luminescence property
Introduction 15 Metal-organic frameworks (MOFs) have attracted consider-
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able attention in recent years owing to their appealing structural topologies and their potential applications as functional materials in absorption,[1,2] molecular recognition,[3,4] gas storage,[5,6] catalysis,[7,8] magnetisms,[9,10] and nonlinear optics.[11,12] Although many strategies have been developed to control the synthesis of MOFs with interesting structures, it is still challenging to predict the exact structures of target products with completely accuracy. In general, the structures of MOFs can be influenced by ligands, metal coordination geometry, inorganic counterion, solvent system, metal saltto-ligand ratio, and temperature. Among these factors, the choice of organic ligands is undoubtedly a key point in the construction of intriguing MOFs.[13–15] N-containing ligands are widely used in the area of supramolecular chemistry for their coordination ability to transition-metal ions and numerous coordination polymers with versatile structures and potential properties have been reported.[16–19] It is well known that the amino group can easily coordinate to metal ions and act as hydrogen-bond acceptors in assembly reactions.[20–22] Although much effort has been made in the study of supramolecular chemistry based on pyridine-containing
Address correspondence to Gui-Ge Hou, School of Pharmacy, Binzhou Medical University, Yantai, Shandong 264003, P. R. China. E-mail:
[email protected] Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsrt.
ligands, amino-functionalized pyridine-containing ligands are less well studied.[23,24] The inclusion of both amino and pyridine functionalized groups can lead to different coordination modes and hydrogen-bonding modes, which may play a 40 crucial role in the construction of supramolecular complexes. Herein we report a 63-nets framework, {[Cd(SiF6) (C11H10N2)2]¢(CH2Cl2)¢(H2O)}n (1), based on cadmium(II) hexafluorosilicate and 3-(pyridin-4-yl)benzenamine (L). In addition, their luminescent properties were investigated 45 primarily.
Experimental Materials and Methods All fluorescence measurements were carried out on a Cary Eclipse Spectrofluorimeter (Varian, Australia) equipped with 50 a xenon lamp and quartz carrier at room temperature. Preparation of 1 A solution of CdSiF6 (2.5 mg, 0.01 mmol) in MeOH (8 mL) was layered onto a solution of L (3.4 mg, 0.02 mmol) in CH2Cl2 (8 mL). The solutions were left for about two weeks 55 at room temperature, and yellow crystals of 1 were obtained. For C23H24CdCl2F6N4OSi, Anal. Calcd. (%:)C 39.58; H 3.46; N 8.02; Found (%): C 39.86; H 3.34; N 8.21. Single-Crystal Structure Determination X-ray intensity data of 1 was measured at 293 K on a Bruker 60 SMART APEX CCD-based diffractometer (Mo Ka
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Table 3. Interatomic distances (A) and bond angles ( ) with esds () for 1.
Table 1. Crystallographic Data for 1. Compound
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Color/shape Formula weight Temperature (K) Crystal system Space group ) a (A ) b (A c (A) Volume (A3) Z m (Mo Ka) (mm¡1) F(000) Crystal size (mm) Theta range for data collection ( ) Reflections collected Independent reflections Data / restraints / parameters Goodness-of-fit on F2 R1, wR2 [I>2sigma(I)] R1, wR2 (all data) a
yellow, block 697.85 298(2) Orthorhombic Fddd 17.3656(8) 24.5676(16) 24.9693(16) 10652.7(11) 16 1.133 5568 0.24£0.20£0.16 1.65–25.50 13420 2482 2482 / 42 / 180 1.032 0.0726, 0.1934 0.0783, 0.2011
R1 D SkFoj¡jFck/SjFoj. wR2 D {S[w(Fo2–Fc2)2]/S[w(Fo2)2]}1/2.
radiation, λ D 0.71073 A). The raw frame data was integrated into SHELX-format reflection files and corrected for Lorentz and polarization effects using SAINT.[25] Corrections for 65 incident and diffracted beam absorption effects were applied using SADABS.[25] Crystal data, data collection parameters, and refinement statistics are listed in Table 1. Relevant interatomic bond distances and bond angles are given in Tables 2 and 3.
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Cd(1)-F(1) 2.290(5); Cd(1)-N(1) 2.322(6); Cd(1)-N(2)#3 2.355(6); F(1)#2-Cd(1)-N(1) 94.7(2); F(1)-Cd(1)-N(1) 86.9(2); N(1)-Cd(1)-N(1)#2 81.7(3); F(1)-Cd(1)-N(2)#3 86.89(19); F(1)-Cd(1)-N(2)#4 91.68(19); N(1)-Cd(1)-N(2)#4 92.0(2); N(2)#3-Cd(1)-N(2)#4 95.1(3) Symmetry codes: #1 x, –y C 3/4, –z C 7/4; #2 –x C 1/4, y, –z C 5/4; #3 x – 1/2, –y C 3/4, –z C 5/4; #4 –x C 3/4, –y C 3/4, z.
CH2Cl2 molecule as free solvent and one water molecule hydrogen-bonded to the -NH2 group of L through the O— H¢¢¢N hydrogen bond (Table 2). The pyridine ring and phenyl ring of L molecule are not coplanar but with a dihedral angle of ca. 16.8 . In the solid state, two ligands are linked by two Cd(II) centers into a 18-membered ring and the distance of the two Cd (II) centers is 9.994 (1) A. The rings further extend into a 1D chain (Figure 2a) via Cd-N bonds along the crystallographic a axis and the corresponding bond lengths [Cd-N(1) D 2.322 (6) A, Cd-N(2) D 2.355 (6) A] are in agreement with the literature reports.[26] The Cd(II) centers are linked by [SiF6]2¡ anions via Cd-F bonds into another kind of 1D chain as each [SiF6]2¡ anion linking two Cd(II) centers (Figure 2b). The distance of two adjacent Cd(II) centers is 7.697 (1) A and the corresponding length of the Cd-F bond is 2.290 (5) A. These 1D chains are linked by Cd(II) centers, which act as connection points into a 3D framework with rectangular channels. As shown in Figure 2c, the arrangement of Cd(II) centers can be described as 63-nets topology.[27] In 1, the disordered CH2Cl2 molecules as free solvents together with water molecules are located in the channels (Figure 3). More interestingly, L molecules, [SiF6]2¡ anions and water molecules are further linked together through the
Results and Discussion Structural Analysis
The X-ray crystal structure shows that 1 is a three-dimensional framework formed by coordination interaction and possesses interesting hydrogen-bonding system. 1 crystallizes 75 in the noncentrosymmetric orthorhombic space group Fddd. Each Cd(II) center lies in a distorted {CdF2N4} octahedral coordination sphere built up of two F atoms from two separate [SiF6]2¡ anions and four N atoms (involving two pyridine N atoms and two amino N atoms) from four separate L 80 molecules (Figure 1). The asymmetric unit also contains one
Table 2. Relevant hydrogen-bonding geometries (A, ) found in 1. D-H. . .A i
O1-H1A¢¢¢F3 O1-H1A¢¢¢F2ii N2-H2B¢¢¢F3iii N2-H2A¢¢¢O1
d(D-H)
d(H. . .A)
d(D. . .A)
