Acetylacetonate Anchors for Robust Functionalization of TiO2 Nanoparticles with Mn(II)-Terpyridine Complexes

被引：136

作者：

McNamara, William R. ^{[1
]}

Snoeberger, Robert C. ^{[1
]}

Li, Gonghu ^{[1
]}

Schleicher, James M., III ^{[1
]}

Cady, Clyde W. ^{[1
]}

Poyatos, Macarena ^{[1
]}

Schmuttenmaer, Charles A. ^{[1
]}

Crabtree, Robert H. ^{[1
]}

Brudvig, Gary W. ^{[1
]}

Batista, Victor S. ^{[1
]}

机构：

[1] Yale Univ, Dept Chem, New Haven, CT 06520 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 43期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1021/ja805498w

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A novel class of derivatized acetylacetonate (acac) linkers for robust functionalization of TiO2 nanoparticles (NPs) under aqueous and oxidative conditions is reported. The resulting surface adsorbate anchors are particularly relevant to engineering pholocatalytic and photovoltaic devices since they can be applied to attach a broad range of photosensitizers and photocatalytic complexes and are not affected by humidity. Acac is easily modified by CuI-mediated coupling reactions to provide a variety of scaffolds, including substituted terpy complexes (terpy = 2,2':6,2 ''-terpyridine), assembled with ligands coordinated to transition-metal ions. Since Mn-terpy complexes are known to be effective catalysts for oxidation chemistry, functionalization with Mn(II) is examined. This permits visible-light sensitization of TiO2 nanoparticles due to interfacial electron transfer, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. The underlying ultrafast interfacial electron injection is complete on a subpicosecond time scale, as monitored by optical pump-terahertz probe transient measurements and computer simulations. Time-resolved measurements of the Mn(II) EPR signal at 6 K show that interfacial electron injection induces Mn(II)-->Mn(III) photooxidation, with a half-time for regeneration of the Mn(II) complex of ca. 23 s.

引用

页码：14329 / 14338

页数：10

共 70 条

[1] Ultrafast photooxidation of Mn(II)-Terpyridine complexes covalently attached to TiO2 nanoparticles [J].