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 6 2016
Accepted
09 9 2016
First published
12 9 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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