三(2,2'-联吡啶)钌(Ⅱ)在磷酸锆层状物中的组装及光物理性质

Assemblies of Tris(2,2'-bipyridyl) Ruthenium(Ⅱ) into Zirconium Phosphate Layered Materials and Their Photophysical Properties

合成了两种层间距极其相近的层状材料Zr(HPO4)2·6H2O(水合α-ZrP)和丁胺-磷酸锆的复合物(α-ZrP·BA),将发光配合物Ru(bpy)32+组装到层状物中使层间距从1.04nm增大到1.52nm.Ru(bpy)32+与层状物相互作用后最大吸收峰均从452nm(水溶液)红移到了462nm.在水合α-ZrP中,最大发射峰位从610nm蓝移到604nm并且荧光强度是水溶液中的两倍多,连续测定4h以后,Ru(bpy)32+的荧光强度仅仅下降了4%;而与α-ZrP·BA相互作用后发射峰位从610nm移动到了595nm,但荧光强度只是稍有增大,4h内强度下降了大约29%;组装到水合α-ZrP中以后,Ru(bpy)32+的激发态寿命从415ns(水溶液)增大到787ns(～95%),在α-ZrP·BA中只增大到了747ns(～89%).这些结果表明层状物水合α-ZrP能够为Ru(bpy)32+光物理性能的改善提供更加优良的微观环境.

Layered materials of zirconium phosphate containing Zr（HPO4）2·6H2O （hydrated α-ZrP） and Zr（HPO4）2.butylammonium （α-ZrP.BA）, which have similar interlayer distance, were prepared. The incor- poration of the luminescent metal complex tris（2,2＇-bipyridyl）ruthenium（Ⅱ） [Ru（bpy）32＋] within the layered materials expands the interlayer distance from 1.04 to 1.52 nm. When the metal complex assembled to the layered frameworks, the absorption band of the complex was red shifted from 452 to 462 nm. In the hy- drated α-ZrP framework, the emission intensity of the complex was over 2-fold compared to that of the same system in aqueous solution and the position of the maximum emission was blue shifted from 610 （aqueous solution） to 604 nm. After the assembly suspension deposited for 4 h, the emission intensity of Ru（bpy）32＋ was reduced by only 4%. However, in α-ZrP·BA, the luminescence intensity of the complex had a little increase and the emission peak was shifted to 595 nm. The emission intensity of Ru（bpy）32＋ decreased by 29% when the suspension was deposited for 4 h. Time-resolved studies manifest that the excited state lifetime of Ru（bpy）32＋ was extended from 415 to 787 ns （-95%） in the hydrated a-ZrP, whereas the lifetime is 747 ns （-89%） in the α-ZrP.BA. These results imply that the hydrated α-ZrP framework provides favorable microenvironment to improve the photophysical properties of Ru（bpY）3^2＋ .