【摘要】 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C2/c和P21/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,β=107.255(2)°,V=1.2931(2)nm3,Z=8,Dc=1.409Mg/m3,F(000)=576,μ(MoKα)=0.102mm-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,β=92.719(3)°,V=1.5860(2)nm3,Z=4,Dc=2.329Mg/m3,F(000)=1072,μ(MoKα)=2.62mm-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(310nm)引起的发射峰有较大的影响.更多还原

【Abstract】 N-Picoloylhydrazide (Hphz) and its binuclear palladium complex [Pd2(phz)2Cl2] were synthe-sized 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, β=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, 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 reflec-tions [I≥σ(I)], wR=0.0555, GOF=0.959. The palladium(II) ion of the complex [Pd2(phz)2Cl2] is coordi-nated 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 in-termolecular 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 (λex=310 nm) were shifted to higher frequencies in fluorescence spectra.更多还原