作为氧化还原试剂的层状无机材料：二茂铁插层磷酸锆。

Layered inorganic materials as redox agents: ferrocenium-intercalated zirconium phosphate.

作者信息

Santiago Mitk'El B, Declet-Flores Chasterie, Díaz Agustín, Vélez Meredith M, Bosques Myrna Zoé, Sanakis Yannis, Colón Jorge L

机构信息

Department of Chemistry, P.O. Box 23346, University of Puerto Rico, Río Piedras, P.R. 00931-3346.

出版信息

Langmuir. 2007 Jul 3;23(14):7810-7. doi: 10.1021/la7005309. Epub 2007 Jun 5.

DOI:10.1021/la7005309

PMID:17547428

Abstract

The direct intercalation reaction of ferrocene (bis(eta5-cyclopentadienyl)iron(II), Fc) with a highly hydrated layered zirconium phosphate (ZrP) resulted in the formation of the ferrocenium ion (Fc+) within the ZrP material. The Fc+-intercalated ZrP material has an interlayer distance of 10.7 A. The intercalated material was used as an electron acceptor for the oxidation of both ferro-cytochrome c and the excited state of tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)3]2+). Upon contact of the material with a 1.5 x 10(-5) M solution of ferro-cytochrome c, the UV-vis absorption spectrum shows the successful formation of ferri-cytochrome c. Luminescence spectroscopy shows that the Fc+-intercalated ZrP material quenches the luminescence of [Ru(bpy)3]2+. The excited-state quenching mechanism of [Ru(bpy)3]2+* by Fc+-intercalated ZrP follows a dynamic plus sphere of action model. The second-order dynamic quenching rate constant kq is 2.2 x 10(8) M(-1) s(-1).

摘要

二茂铁（双（η5-环戊二烯基）铁（II），Fc）与高度水合的层状磷酸锆（ZrP）的直接插入反应导致在ZrP材料中形成二茂铁鎓离子（Fc+）。插入了Fc+的ZrP材料的层间距为10.7埃。该插入材料用作电子受体，用于氧化亚铁细胞色素c和三（2,2'-联吡啶）钌（II）（[Ru（bpy）3]2+）的激发态。当该材料与1.5×10（-5）M的亚铁细胞色素c溶液接触时，紫外可见吸收光谱表明成功形成了高铁细胞色素c。发光光谱表明，插入了Fc+的ZrP材料猝灭了[Ru（bpy）3]2+的发光。Fc+插入的ZrP对[Ru（bpy）3]2+*的激发态猝灭机制遵循动态加作用球模型。二级动态猝灭速率常数kq为2.2×10（8）M（-1）s（-1）。