N-皮考林酰肼及其双核钯配合物的晶体结构和荧光性质  

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

作　　者：吴文士[1] 陈静[1] 戴劲草[1] 林建明[1] 蓝心仁[1] 黄婷婷[1] 

机构地区：[1]华侨大学材料学院,泉州362021

出　　处：《化学学报》2005年第21期1967-1973,共7页Acta Chimica Sinica

基　　金：福建省重大科技基金(No.2003F006);福建省自然科学基金(No.E0210026)资助项目.

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.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, β= 107.255（2）°, V= 1.2931（2） nm^3, Z=8, Dc= 1.409 Mg/m^3, 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]（C12H12C12N6O2Pd2）, 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）nm^3, Z=4, Dc=2.329 Mg/m^3, 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, v（C=O） and v（C=N） were shifted to lower frequencies and v（C-N） was shifted to higher frequencies in IR spectra. The emission lines （λex=310 nm） were shifted to higher frequencies in fluorescence spectra.

关 键 词：晶体结构 N-皮考林酰肼 双核钯配合物 钯配合物 荧光性质 双核 酰肼 量子化学从头算方法 分子间氢键 X射线衍射实验 

分 类 号：O641.4[理学—物理化学]