Department of Chemistry, Rice University, 6100 S Main Street, MS-60, Houston, Texas 77005, USA.
Inorg Chem. 2010 Aug 16;49(16):7298-303. doi: 10.1021/ic902419z.
We studied the structures, luminescence, and self-quenching properties of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) two-dimensional arrangements within the layers of zirconium phosphate (ZrP). The intercalation of Ru(bpy)(3)(2+) was accomplished using a hydrated form of zirconium phosphate ZrP. Varying the Ru(bpy)(3)(2+)/ZrP intercalation ratio, different Ru(bpy)(3)(2+)-exchanged ZrP loading levels were achieved. The ion exchange of Ru(bpy)(3)(2+) within ZrP produces a red shift in the metal-to-ligand charge-transfer (MLCT) absorption band of the complex from 452 nm in aqueous solution to 460 nm in ZrP. Steady state luminescence spectra of the Ru(bpy)(3)(2+)-exchanged ZrP materials show an increase in the luminescence intensity with an increase in the Ru(bpy)(3)(2+) loading level until about 0.77 M, where subsequent increases in the loading level produce a decrease in the luminescence (self-quenching region). Time-resolved luminescence measurements are consistent with the steady state luminescence measurements. Analysis of the time domain luminescence measurements in loadings higher than 0.77 M leads to the determination of a collisional quenching rate constant of (1.67 +/- 0.05) x 10(6) M(-1) s(-1). Stern-Volmer analysis of the luminescence quantum yield of Ru(bpy)(3)(2+)-exchanged ZrP materials indicates that static quenching is also involved in the Ru(bpy)(3)(2+) self-quenching mechanism. The quantum yield data behavior might be explained by a model that takes into account collisional quenching and the quasi-static Perrin mechanism. The calculation yields a quenching sphere of action of 14.8 A, which is slightly larger than the collisional radii of two Ru(bpy)(3)(2+) ions (12.2 A), as predicted by the model.
我们研究了三(2,2'-联吡啶)钌(II)(Ru(bpy)(3)(2+))在磷酸锆(ZrP)层内二维排列的结构、发光和自猝灭性质。Ru(bpy)(3)(2+)的嵌入是通过使用水合形式的磷酸锆 ZrP 来完成的。通过改变 Ru(bpy)(3)(2+)/ZrP 的嵌入比，可以获得不同的 Ru(bpy)(3)(2+)交换 ZrP 负载水平。在 ZrP 中，Ru(bpy)(3)(2+)的离子交换导致配合物的金属-配体电荷转移(MLCT)吸收带从水溶液中的 452nm 红移到 ZrP 中的 460nm。Ru(bpy)(3)(2+)交换的 ZrP 材料的稳态荧光光谱显示，随着 Ru(bpy)(3)(2+)负载水平的增加，荧光强度增加，直到约 0.77M，随后负载水平的增加导致荧光降低(自猝灭区域)。时间分辨荧光测量与稳态荧光测量一致。在负载高于 0.77M 的情况下，对时域荧光测量的分析导致确定了一个碰撞猝灭速率常数为(1.67 +/- 0.05) x 10(6) M(-1) s(-1)。Ru(bpy)(3)(2+)交换的 ZrP 材料的荧光量子产率的 Stern-Volmer 分析表明，静态猝灭也参与了 Ru(bpy)(3)(2+)的自猝灭机制。量子产率数据的行为可以用一个模型来解释，该模型考虑了碰撞猝灭和准静态 Perrin 机制。计算得到的猝灭球半径为 14.8A，略大于模型预测的两个 Ru(bpy)(3)(2+)离子的碰撞半径(12.2A)。
