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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (21): 1967-1973. 上一篇    下一篇

研究论文

N-皮考林酰肼及其双核钯配合物的晶体结构和荧光性质

吴文士*，陈静，戴劲草，林建明，蓝心仁，黄婷婷   

  1. (华侨大学材料学院 泉州 362021)
  • 投稿日期:2005-02-24 修回日期:2005-07-20 发布日期:2010-12-10
  • 通讯作者: 吴文士

Crystal Structure and Fluorescence of N-Picoloylhydrazide and Its Binuclear Palladium Complex

WU Wen-Shi*, CHEN Jing, DAI Jing-Cao, LIN Jian-Ming, LAN Xin-Ren, HUANG Ting-Ting   

  1. (College of Material, Huaqiao University, Quanzhou 362021)
  • Received:2005-02-24 Revised:2005-07-20 Published:2010-12-10
  • Contact: WU Wen-Shi

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合成了配体N-皮考林酰肼(简写为Hphz)及其双核钯配合物[Pd2(phz)2Cl2]. X射线衍射实验结果表明, 配体和配合物晶体均属于单斜晶系, 空间群分别为C 2/c和P 21/c, 分子式分别为C6H7N3O和C12H12Cl2N6O2Pd2. 晶体学参数, Hphz, a＝1.9245(2) nm, b＝0.38927(2) nm, c＝1.8073(2) nm, b＝107.255(2)°, V＝1.2931(2) nm3, Z＝8, Dc＝1.409 Mg/m3, F(000)＝576, μ(Mo Kα)＝0.102 mm－1, R＝0.0541, wR＝0.1762; [Pd2(phz)2Cl2], a＝1.48274(9) nm, b＝1.44797(9) nm, c＝0.73951(5) nm, b＝92.719(3)°, V＝1.5860(2) nm3, Z＝4, Dc＝2.329 Mg/m3, F(000)＝1072, μ(Mo Kα)＝2.62 mm－1, R＝0.0262, wR＝0.0555. 在配合物[Pd2(phz)2Cl2]分子内, 两个钯(II)原子, 均呈畸变的N3Cl平面正方形配位构型, 晶体内通过分子间氢键N—H…Cl 作用形成一维链状结构, 分子间吡啶环存在相互作用. 量子化学从头算方法计算结果表明, 分子内及分子间的金属钯之间也存在相互作用. 红外光谱表明, 配体在形成配合物后, ν(C＝O)和ν(C＝N)红移, ν(C—N)蓝移, 荧光光谱表明, 配合物金属对配体n-π*激发(310 nm)引起的发射峰有较大的影响.

关键词: 晶体结构, N-皮考林酰肼, 双核钯配合物

N-Picoloylhydrazide (Hphz) and its binuclear palladium complex [Pd2(phz)2Cl2] were synthesized and determined by single crystal X-ray diffraction. They belong to monoclinic system. Crystal data: Hphz(C6H7N3O), space group C2/c, a＝1.9245(2) nm, b＝0.38927(2) nm, c＝1.8073(2) nm, b＝107.255(2)°, V＝1.2931(2) nm3, Z＝8, Dc＝1.409 Mg/m3, F(000)＝576, m(Mo Kα)＝0.102 mm－1, 0.0541 for 1257 observed reflections [I≥σ(I)], wR＝0.1762, GOF＝1.124; [Pd2(phz)2Cl2](C12H12Cl2N6O2Pd2), space group P21/c, a＝1.48274(9) nm, b＝1.44797(9) nm, c＝0.73951(5) nm, β＝92.719(3)°, V＝1.5860(2) nm3, Z＝4, Dc＝2.329 Mg/m3, F(000)＝1072, μ(Mo Kα)＝2.62 mm－1, R＝0.0262 for 2937 observed reflections [I≥σ(I)], wR＝0.0555, GOF＝0.959. The palladium(II) ion of the complex [Pd2(phz)2Cl2] is coordinated with two pyridine nitrogen atom and two diazine nitrogen atom, forming a distorted square geometry. Pd…Pd distance is 0.38111 nm in the complex. There is a one-dimensional chain structure through the intermolecular hydrogen bonds N—H…Cl in complex crystal. There are π-π interactions in the neighboring ligands. The ab initio calculation with Hartree-Fork method showed that there are interactions between Pd and Pd in the complex molecule and the neighboring molecule. ν(C＝O) and ν(C＝N) were shifted to lower frequencies and ν(C—N) was shifted to higher frequencies in IR spectra. The emission lines (lex＝310 nm) were shifted to higher frequencies in fluorescence spectra.

Key words: crystal structure, N-picoloylhydrazide, binuclear palladium complex