Issue 11, 2016

Spectroscopic and electrochemical properties of ruthenium complexes with photochromic triarylamine–dithienylethene–acetylide ligands

Abstract

A new dithienylperfluorocyclopentene–acetylide ligand (L2o) appended with a triarylamine moiety was used to synthesize two ruthenium(II) complexes with a photoswitchable electronic interaction between inorganic (Ru) and organic (triarylamine) redox centres. The reactions of cis-Ru(dppe)2Cl2 with one or two equiv. of L2o produce trans-Ru(dppe)2(L2o)Cl (1o) or trans-Ru(dppe)2(L2o)2 (2oo), respectively. As demonstrated by 1H and 31P NMR spectral studies, 2oo shows stepwise photocyclization leading first to the singly ring-closed species 2co, and then to the doubly ring-closed species 2cc upon irradiation at 312 nm. Complex 1o exhibits two separated anodic waves at 0.60 (RuII/III) and 0.86 V (N0/+) caused by inherent redox dissymmetry and electronic interaction. Upon conversion to the ring-closed species 1c, three reversible anodic waves are found at 0.28, 0.37 and 0.66 V due to the oxidation of the ring-closed DTE, triarylamine and Ru, respectively. One-electron oxidized species [1c]+ displays broad and moderately intense absorption bands in the near-infrared region induced by charge delocalization. For the oxidized species [2oo]2+/[2co]2+/[2cc]2+, charge delocalization along the molecular backbone shows a progressive increase following the stepwise photocyclization process.

Introduction to the international collaboration

Zhong-Ning Chen and Denis Jacquemin launch a collaborative research project on multi-photochromism in metal complexes encompassing several photochromic moieties. The group of Chen is devoted to the experimental synthesis and characterization of metal coordinated systems with multi-photochromic dithienylethene (DTE) moieties and the use of stepwise or selective photochromism to modulate switchable electronic communication and charge delocalization in heterometallic or inorganic–organic mixed-valence systems. Jacquemin's group focuses on theoretical investigation of the mechanism underlying the multi-photochromism through a time dependent density functional theory (TD-DFT) approach, taking into account when necessary spin–orbit couplings (SOC) so as to model potential intersystem crossings (ISC).

Graphical abstract: Spectroscopic and electrochemical properties of ruthenium complexes with photochromic triarylamine–dithienylethene–acetylide ligands

Supplementary files

Article information

Article type
Research Article
Submitted
07 जून 2016
Accepted
09 सितम्बर 2016
First published
12 सितम्बर 2016

Inorg. Chem. Front., 2016,3, 1432-1443

Spectroscopic and electrochemical properties of ruthenium complexes with photochromic triarylamine–dithienylethene–acetylide ligands

D. Zhang, J. Wang, D. Jacquemin and Z. Chen, Inorg. Chem. Front., 2016, 3, 1432 DOI: 10.1039/C6QI00175K

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