Jump to main content
Jump to site search

Issue 18, 2015
Previous Article Next Article

A tricarboxylated PtCl(terpyridine) derivative exhibiting pH-dependent photocatalytic activity for H2 evolution from water

Author affiliations

Abstract

The first negatively charged PtCl(tpy) (tpy = 2,2′:6′,2′′-terpyridine) derivative, formulated as Na2[PtCl(tctpy)]·5H2O (tctpy = 2,2′:6′,2′′-terpyridine-4,4′,4′′-tricarboxylate), was prepared, characterized, and investigated in detail for its activity as a single-component photocatalyst that drives water reduction to H2 in the presence of a sacrificial electron donor (EDTA). This compound was confirmed to exist in its fully deprotonated form [PtCl(tctpy)]2− in aqueous media at pH > 4.4. Despite its dianionic character, [PtCl(tctpy)]2− was found to form a specific adduct with anionic EDTA (i.e., YH22− and YH3−, where YH4 is a fully protonated form of EDTA), enabling reductive quenching of the triplet metal-to-ligand charge transfer excited state within the adduct, leading to subsequent electron transfer steps correlated with Pt(II)-catalyzed H2 evolution from water. Electrochemical studies also reveal that the compound exhibits a unique pH-dependent first reduction (i.e., tctpy-centered reduction), leading to our realization of the first example of a Pt(II)-based molecular system that photocatalyzes the H2 evolution reaction accompanied by a ligand-based proton-coupled electron transfer (PCET) process.

Graphical abstract: A tricarboxylated PtCl(terpyridine) derivative exhibiting pH-dependent photocatalytic activity for H2 evolution from water

Back to tab navigation

Supplementary files

Publication details

The article was received on 29 Jan 2015, accepted on 23 Mar 2015 and first published on 23 Mar 2015


Article type: Paper
DOI: 10.1039/C5DT00425J
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2015,44, 8685-8696
  •   Request permissions

    A tricarboxylated PtCl(terpyridine) derivative exhibiting pH-dependent photocatalytic activity for H2 evolution from water

    K. Yamauchi and K. Sakai, Dalton Trans., 2015, 44, 8685
    DOI: 10.1039/C5DT00425J

Search articles by author

Spotlight

Advertisements