2,6-双二苯基膦吡啶银(Ⅰ)配合物的光谱研究

Spectroscopic Study on 2,6-bis(diphenylphosphino)pyridine Ag(Ⅰ) Complex

利用电子吸收光谱和发射光谱 ,研究具有光致发光性能的三配位Ag (Ⅰ )配合物[Ag2 (μ PNP) 3](ClO4 ) 2 (PNP =2 ,6 双二苯基膦吡啶 )的光谱性质 ,电子吸收光谱中约 2 6 0和 30 0nm处的肩峰吸收分别被指定为l→aπ(l代表膦的孤对电子 ,aπ 是苯环的反键轨道 )和l→π (π 表示吡啶的π反键轨道 )跃迁。室温下受紫外可见光激发 ,配合物的乙腈溶液显示了发光性质 ,其发射峰位于 5 2 5nm ,这是由配体激发态引起的。利用吸收和发射光谱 ,研究了配合物光物理性质在不同客体分子如AuPPh3Cl,AgCF3SO3和 [Cu(CH3CN) 4](ClO4 )存在下光物理性质的改变情况。在配合物中 ,配体PNP和Ag(Ⅰ )形成一个空穴 ,可以结合外来的离子 ,从而引起光物理性质的改变 ,这种改变 ,使 [Ag2 (μ PNP) 3](ClO4 ) 2 可以作为作为客体离子的检测探针或传感器。

The spectroscopic properties of a three coordinate Ag(Ⅰ) photoluminescent complex [Ag 2( μ PNP) 3](ClO 4) 2, PNP=2, 6 bis(diphenylphosphino)pyridine, were studied. The electronic shoulder absorptions of the complex around 260 and 300 nm have been assigned to l→a π(l stands for lone pair electron and a π for anti bonding orbital of benzene ring) and l→π *(π * for anti bonding orbital of pyridyl) transitions, respectively. In acetonitrile, the complex exhibited luminescence with an emission peak at 525 nm upon excitation with UV Vis light at room temperature. The excited state was intraligand in nature. The photophysical properties of the complex, altering in the presence of different guest molecules, such as AuPPh 3Cl, AgCF 3SO 3 and [Cu(CH 3CN) 4](ClO 4), were explored by using electronic absorption and emission spectrometry. In the complex, the ligand PNP and Ag(Ⅰ) ions formed an open cavity and were capable of binding a second, different ion. The substantial change of photophysical properties in the presence of different guest molecules suggests that [Ag 2( μ PNP) 3](ClO 4) 2 can be used as a probe or sensor for these guest ions.