Jump to main content
Jump to site search


Excited state relaxation processes of H2-evolving Ru–Pd supramolecular photocatalysts containing a linear or non-linear bridge: a DFT and TDDFT study

Author affiliations

Abstract

In this study, the early-time excited state relaxation processes of bimetallic Ru–Pd supramolecular photocatalysts containing a linear 2,2′:5′,2′′-terpyridine or a nonlinear 2,2′:6′,2′′-terpyridine bridging ligand (BL) were investigated by density functional theory (DFT) and time-dependent DFT (TDDFT) approaches. The bridge based metal-to-ligand charge transfer triplet (3MLCT) state of the metal complex containing a linear bridging ligand was calculated to be the lowest energy triplet (T1) state which is closely related to the photocatalytic H2 production, while for that having a nonlinear bridging ligand, the T1 state is a Ru metal-centered (MC) triplet (3MCRu) state that is short-lived and rapidly decays to the ground electronic state (S0). Our simulation provides an alternative explanation for the smaller interligand electron transfer (ILET) rate in the Ru–Pd complex containing a linear bridge compared to the corresponding monometal Ru complex. Based on the calculation, we also suggest that the successive 3MLCT → 3MCRu → S0 conversion is responsible for the inefficiency of the Ru–Pd complex containing nonlinear bridge as a photocatalyst for H2 production. This study provides theoretical insights into the key steps of the photoinduced processes of the bimetallic H2-evolving supramolecular photocatalyst.

Graphical abstract: Excited state relaxation processes of H2-evolving Ru–Pd supramolecular photocatalysts containing a linear or non-linear bridge: a DFT and TDDFT study

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 17 Nov 2016, accepted on 28 Mar 2017 and first published on 05 Apr 2017


Article type: Paper
DOI: 10.1039/C6CP07857E
Citation: Phys. Chem. Chem. Phys., 2017, Advance Article
  •   Request permissions

    Excited state relaxation processes of H2-evolving Ru–Pd supramolecular photocatalysts containing a linear or non-linear bridge: a DFT and TDDFT study

    J. Cao and Y. Zhou, Phys. Chem. Chem. Phys., 2017, Advance Article , DOI: 10.1039/C6CP07857E

Search articles by author