Issue 6, 2017

An unprecedented photochromic system with cis-oriented dithienyl-dithiolenes supported by metal chelation

Abstract

4,5-Bis(2-methyl-5-phenylthiophen-3-yl)-1,3-dithiol-2-one (L1o) was elaborately designed to afford dithienyl-dithiolene as a new photochromic ligand. We describe herein the preparation and characterization of unprecedented photochromic dithienyl-dithiolene complexes with cis-orientation of dithienylethene (DTE) stabilized by metal chelation instead of conventional cyclopentene. The treatment of L1o with sodium methoxide in methanol afforded a disodium salt of dithiolate dianion, which reacts with M(dppe)Cl2 (dppe = 1,2-bis(diphenylphosphino)ethane, M = Ni, Pd) to give neutral compounds M(dppe)(dithiolate) as established by X-ray crystallography. The reaction of L1o with NiCl2 in the presence of sodium methoxide allows the isolation of an anionic nickel(II) bis(dithienyl-dithiolene) complex with photochemical inertness. In contrast, the corresponding reaction with ZnCl2 afforded a dianionic zinc(II) complex chelated by two dianionic dithienyl-dithiolenes, which displays stepwise photocyclization upon irradiation with UV light at 312 nm as demonstrated experimentally and theoretically. Only when dithienyl-dithiolene behaves as a dicationic ligand instead of neutral or monoanionic species, it is possible to achieve reversible photochromism in the corresponding metal complexes.

Graphical abstract: An unprecedented photochromic system with cis-oriented dithienyl-dithiolenes supported by metal chelation

Supplementary files

Article information

Article type
Paper
Submitted
22 Nov 2016
Accepted
18 Jan 2017
First published
18 Jan 2017

Dalton Trans., 2017,46, 2023-2029

An unprecedented photochromic system with cis-oriented dithienyl-dithiolenes supported by metal chelation

J. Wang, L. Shi, J. Wang, J. Chen, S. Liu and Z. Chen, Dalton Trans., 2017, 46, 2023 DOI: 10.1039/C6DT04421B

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