[Cd(p-nitrobenzoic acid)2(en)H2O] coordination compound in structure and fluorescent property
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摘要: 以氯化镉、对硝基苯甲酸和乙二胺（en）为原料，成功合成了具有荧光性能的[Cd（对硝基苯甲酸）2（乙二胺）H2O]配合物 1 ，并对其结构进行解析。首先，采用水热合成法进行配合物 1 的合成。接着，利用单晶X射线衍射测定配合物 1 的结构。然后，采用元素分析法、红外光谱法（IR）、热重分析法（TGA）和粉末X射线衍射法（PXRD）对其进行表征。最后，在室温条件下，对配合物 1 进行荧光性能测试。实验结果表明：配合物 1 通过N-H…O、O-H…O和C-H…O氢键将离散结构连接形成三维超分子构型。配合物 1 在266 nm处激发，在377 nm和444 nm处出现两个发射峰，表现出较强的荧光性能。上述结果说明，配合物 1 的荧光性能主要来自于配体到配体的跃迁，可以作为具有发展潜能的荧光光学材料。Abstract: In this paper, a new coordination polymer of[Cd(p-nitrobenzoic acid)2(en)H2O]( 1 ) was synthesized, based on CdCl2, p-nitrobenzoic acid and ethylenediamine(en), and its structure was analyzed. First, a compound(compound 1 ) was hydrothermally synthesized. Second, compound 1 was structurally measured using single-crystal X-ray diffraction. Then, compound 1 was structurally characterized using infrared spectrometry(IR), elemental analysis, power X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). Finally, the fluorescence property of compound 1 was measured at room temperature. Experimental results indicate that compound 1 was linked into a three-dimensional(3D) supramolecular structure by N-H…O、O-H…O and C-H…O hydrogen bonds. Compound 1 demonstrated fluorescent properties. Its peak of excitation was 266 nm and its peaks of emission were 377 nm and 444 nm. The fluorescent properties of compound 1 mainly come from the transition from the ligand to ligand. Compound 1 may be a fluorescent material with potential for further development.
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Key words:
- p-nitrobenzoic acid /
- hydrogen bonds /
- supramolecular structure
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图 1 配合物1的不对称结构单元(对称码：i.x, 0.5-y, z)
Figure 1. Asymmetric structure of compound 1 (symmetry code: # i, x, 0.5-y, z)
图 2 (a) 一维链状结构；(b)二维层状结构；(c)三维超分子结构(对称码：ii, 1-x, -0.5+y, 1-z; iii, 1+x, 0.5-y, z; iv, 0.5+x, y, 0.5-z; v, 0.5+x, 0.5-y, 0.5-z; vi, 2-x, 1-y, 1-z)
Figure 2. (a)1D chain structure; (b)2D layer structure; (c)3D supramolecular structure(symmetry codes:ii, 1-x, -0.5+y, 1-z; iii, 1+x, 0.5-y, z; iv, 0.5+x, y, 0.5-z; v, 0.5+x, 0.5-y, 0.5-z; vi, 2-x, 1-y, 1-z)
图 7 室温条件下配合物1的荧光谱图
Figure 7. Photoluminescence spectra of compound 1 at room temperature
表 1 配合物1的晶体学数据
Table 1. Crystal parameters and structural optimization parameters for compound 1
配合物1 参数 分子式 C16H18CdN4O9 晶系 斜方晶系 分子量 522.74 体积/nm3 1.939 9(6) 空间群 Pnma 温度/K 296(2) Z 4 a/nm 0.618 31(11) F(000) 1 048 b/nm 2.236 1(4) θ范围/(°) 1.713~28.145 c/nm 1.403 1(3) Dc/(Mg·m-3) 1.790 α/(°) 90 GOF 1.024 β/(°) 90 μ/mm-1 1.185 γ/(°) 90 R值(全部数据) R1=0.040 2, wR2=0.063 3 独立衍射点(Rint) 2 417(0.031 2) Ra, b值[I > 2σ(I)] R1=0.027 3, wR2=0.057 4 收集衍射点 11 300 
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表 2 配合物1的主要化学键的键长(nm)和键角(°)
Table 2. Main bond lengths(nm) and bond angles(°) in compound 1
化学键 键长/nm 化学键 键长/nm 化学键 键长/nm Cd1-O1 0.255 4(2) Cd1-O2 0.234 7(2) Cd1-O5 0.231 1(3) Cd1-N1 0.234 1(3) Cd1-N2 0.229 4(3) Cd1-O1i 0.255 4(2) Cd1-O2i 0.234 7(2) 化学键 键角(°) 化学键 键角(°) 化学键 键角(°) O1i-Cd1-O1 172.00(9) O2-Cd1-O1i 135.03(7) O2i-Cd1-O1 135.03(7) O2i-Cd1-O2 82.19(9) O2i-Cd1-O1i 52.85(6) O2-Cd1-O1 52.85(6) O5-Cd1-O1i 89.50(6) O5-Cd1-O1 89.50(6) O5-Cd1-O2i 88.24(10) O5-Cd1-O2 88.24(10) O5-Cd1-N1 172.25(12) N1-Cd1-O1 89.96(6) N1-Cd1-O1i 89.96(6) N1-Cd1-O2 97.58(7) N1-Cd1-O2i 97.58(7) N2-Cd1-O1 86.09(5) N2-Cd1-O1i 86.09(5) N2-Cd1-O2i 138.82(4) N2-Cd1-O2 138.82(4) N2-Cd1-O5 95.21(13) N2-Cd1-N1 77.04(10) 对称码：i.x, 0.5-y, z.
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表 3 配合物1氢键键长(nm)和键角(°)
Table 3. Hydrogen bond distances(nm) and angles(°) in compound 1
D-H d(D-H) d(H…A) ∠DHA d(D-A) A N1-H1 0.089 0.232 168 0.320 2(3) O4ii N2-H2 0.089 0.242 155 0.324 5(3) O2iii O5-H5A 0.077 0.222 133 0.279 7(3) O2iv O5-H5B 0.089 0.248 101 0.279 7(3) O2v C2-H2A 0.097 0.242 109 0.288 6(5) O4vi 对称码:ii, 1-x, -0.5+y, 1-z; iii, 1+x, 0.5-y, z; iv, 0.5+x, y, 0.5-z; v, 0.5+x, 0.5-y, 0.5-z; vi, 2-x, 1-y, 1-z.
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