WANG Qing-Wei CHEN Lin QI Xiao-Fei WANG Ya-Nan LIU Bo

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A 3-fold Interpenetrated lvt Cd(II) Network Constructed from 4-[(3-pyridyl)methylamino]benzoate Acid①

WANG Qing-Wei②CHEN Lin QI Xiao-Fei WANG Ya-Nan LIU Bo

(136000)

A new three-dimensional (3D) coordination polymer, [Cd(L)2H2O]n·5nH2O1 with 4-[(3-pyridyl)methylamino]benzoate acid (HL),has been synthesized by slow evaporation solvent at room temperature, and structurally characterized by elemental analysis, IR spectrum, thermal analysis, fluorescence spectrum and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system, space group-4, with= 20.7937(16),= 13.515(2),= 5843.5(11) ?3, C26H34CdN4O10,M= 674.97,D= 1.534 g/cm3,(Mo) = 0.808 mm-1,(000) = 2768,= 8, the final= 0.0276 and= 0.0691 for 5323 observed reflections (> 2()). The result of thermal analysis shows that 1 is stable under290 ℃. Moreover, it exhibits blue photoluminescence at room temperature.

4-[(3-pyridyl)methylamino]benzoate acid, lvt topology, 3-fold interpenetrated, luminescent property

1 INTRODUCTION

2 EXPERIMENTAL

2. 1 General procedures

HL was synthesized by the procedure reported[28],and other reagents and solvents employed were commercially available and used as received.Ele- mental analyses (C, H, N) were carried out with a Perkin-Elmer 2400 CHN elemental analyzer. In- frared (IR) spectra were obtained on a Perkin- Elmer Spectrum One instrument as KBr pellets (4000～400 cm-1). The TG analysis was conducted on a Perkin-Elmer Diamond TG/DTA 6300 thermal ana- lyzer. The solid-state photoluminescent spectra were recorded on a Perkin-Elmer LS-55 Fluorescence Spectrometer at room temperature.

2. 2 Synthesis of [Cd(L)2H2O]n·5nH2O

The title compound was prepared from the following method: Cd(NO3)2·4H2O (0.046 g, 0.15 mmol) and HL (0.068 g, 0.3 mmol) were add to 20 mL water in a beaker. The mixture was stirred until dissolve and NH3·H2O(35 drops) was dropwise added to give a clear solution followed by final filtration. The filtrate was allowed to concentrate slowly by evaporation at room temperature. Several days later, colorless block crystalsof 1 were obtained by filtration and washed with distilled water in 26% yield (based on Cd). Anal. Calcd. (%) forC26H34CdN4O10: C, 46.3; H, 5.1; N, 8.3. Found (%): C, 46.1; H, 4.9; N, 8.2. IR (KBr, cm-1): 3410s, 1608m, 1523m, 1389s, 1323s, 1279s, 1241s, 1141s, 1109m, 1080s, 1051s, 1034s, 861s, 841s, 782m, 706m, 631m.

2. 3 X-ray structure determination

A single crystal of 1with dimensions of 0.40mm′0.37mm′0.34mm was chosenand mounted on a glass fiber. All the data were collected with a Bruker CCD diffractometer equipped with a graphite-mo- nochromatic Mo(= 0.71073 ?) radiation using anscan mode at 293(2) K. In the range of 3.60<2<51.82o, a total of 15877reflections were collected and 5680 were independent withint= 0.0226,of which 5323were observed with> 2(). The correction forfactors was applied. The structure was solved by direct methods with the program SHELXS-97[29]and refined by full-matrix least-squares methods on2with SHELXL-97[30]. Non-hydrogen atoms were refined with anisotropic temperature parameters, and hydrogen atoms of the ligands were refined as rigid groups. The hydrogen atoms associated with water molecules were not located from the difference Fourier maps. The final= 0.0276 and= 0.0691 (= 1/[2(F2) + (0.0438)2+ 0.0000], where= (F2+ 2F2)/3).= 1.053, (Δ)max= 0.379, (Δ)min= –0.222 e/?3and (Δ/)max= 0.001. The selected bond lengths and bond angles are given in Table 1.

Table 1. Selected Bond Lengths (?) and Bond Angles (°) for 1

Symmetry transformations used to generate the equivalent atoms: A:+1, –+1, –+2; B:+3/2, –+1/2, –+1/2

3 RESULTS AND DISCUSSION

3. 1 IR spectrum

The COO–is coordinated with its asymmetric and symmetric stretching appearing at 1608 cm–1((OCO)assym) and 1523 cm–1((OCO)sym)[31], re- spectively. The Δ((OCO)assym–(OCO)sym) is 85 cm–1(< 200), showing the presence of bidentate linkage of carboxylates in the dianions. Thus, the carboxylates coordinate to the metal as bidentate ligandsthe carboxylate groups[32]. The absence of characteristic bands around 1700 cm-1in com- pound 1 attributed to the protonated carboxylic group indicates the complete deprotonation of HL ligand upon reaction with the Cd ions[33]. In addition, X-ray diffraction analysis further indicates the bidentate coordinationmanners of carboxylate groups and the deprotonation of HL ligands.

3. 2 Description of the structure

Single-crystal X-ray diffraction analysis reveals that 1crystallizes in tetragonal crystalsystemand space group-4. It exhibits a fascinating 3D poly- meric architecture consisting of three equivalent interpenetratingnets of lvt topology. As illustrated in Fig. 1, the asymmetric unit of 1 contains one Cd ion, two L anions, one coordinated water molecule and five freewater molecules.The seven-coordinated Cd ion is surrounded by four carboxylate oxygen atoms from two different L ligands, two nitrogen atoms from two different L ligands, and one coordinated water molecule, which belongs to distorted penta- gonal-bipyramidal coordination geometry.Topolo- gically,each Cd ion is coordinated by four ligands as a four-connected node, and each ligand links two Cd ions, generating a 3D framework with lvt topology (Point Symbol 4284)[34-43], as shown in Fig. 2(a). In spite of the same Cd ion and L ligand, it is geome- trically and topologically quite different to other reported compounds[28].

Fig. 1. Thermal ellipsoids (40% probability) representation of 1. Hydrogen atoms and free waters were omitted for clarity. Symmetry codes: (A)+1, –+1, –+2; (B)+3/2, –+1/2, –+1/2

Fig. 2. (a) Schematic presentations of a single 3D net of 1:4-connected lvt net. (b) Views of three connected rhombi of a single 3D net in 1

In a single 3D net, each four-connected node generates two types of rhombic cavities; one is a planar eight-membered circuit with a very large cavity (ca. 45.57? × 20.79?), and the other is a nonplanar four-membered circuit. The planar square- grids (red and blue) are fused together by sharing metal atoms at the midpoints of the rhombic edges, generating the four-membered rings (Fig. 2(b)). The sizes of the eight-membered circuit are so large that they allow 3-fold interpenetration to occur (Fig. 3). Itis similar to the reported compound [Cu(L)- (DMF)·5/2H2O]n(L = 4,4?-dicarboxydiphenyl- amine)[44].

Fig. 3. Schematic view of the 3-fold parallel interpenetration in 1

Hydrogen bonding interactions are usually impor- tant in the synthesis of supramolecular architec- ture[45]. There are persistent N–H···O hydrogen bon- ding interactions between crystal water molecules andnitrogen atom of L ligands (N(4)···O(5W) = 2.982(7) ?, N(4)–H(4A)···O(5W) = 164o), which undoubtedly play an important role in stabilizing compound 1.

首先，通過溴代物與硫代羧酸之間的親核取代反應(yīng)合成了兩種含羧基結(jié)構(gòu)的雙硫酯(1，2)，兩者的合成路線如圖1所示。

3. 3 Thermogravimetric analysis

Thermogravimetric analysis (TGA) was perfor- med to examine the thermal stability of 1. The crushed single crystal sample was heated up to 600 ℃under N2gas at a heating rate of 10 ℃?min-1. As shown in Fig. 4, the first weight loss of 15.68% occurs between room temperatureand 290 ℃, cor- responding to the removal of water molecules (calcd. 16.01%). In the range of 290～460 ℃, the second weight loss of67.80% can be ascribed to the release of organic ligands (calcd.67.30%). TGA results basically agree with the formula of compound 1. Theabove thermal behaviors may be attributed to the structural features.

Fig. 4. TGA curve of 1 from room temperature to 600 ℃

3. 4 Photoluminescent properties

Recently, CPs with10metal centers have attrac- ted much attention due to there potential applications such as in chemical sensors, photochemistry, and electroluminescent display[46-48]. Hence, the photo- luminescentproperty ofcompound 1 has been in- vestigated in the solid state at room temperature (Fig. 5). Compound 1 exhibits blue fluorescence with maximum emission at 437 nm (ex= 330 nm). The Cdion is difficult to oxidize or to reduce due to the10configuration, so the emission is neither MLCT nor LMCT[49-52]. As a result, the emission can probably be assigned to intraligand transitions.

Fig. 5. Solid-state emission spectrum of the title compound at room temperature

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7 November 2013;

3 May 2014 (CCDC 932708)

① The project was supported by the Science and Technology Development Project of Jilin Provincial Science & Technology Department (201205080) and the Science and Technology Research Projects of the Education Office of Jilin Province (No. 2013. 384)

. Wang Qing-Wei, born in 1961. Tel: 0434-3291973, E-mail: wqw611223@163.com