NDLI: An unprecedented photochromic system with <i>cis</i>-oriented dithienyl-dithiolenes supported by metal chelation

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

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Dalton Transactions Vol - 46 Issue - 5

Dalton Transactions Vol - 46 Issue - 4

Dalton Transactions Vol - 46 Issue - 3

Dalton Transactions Vol - 46 Issue - 2

Dalton Transactions Vol -39

Dalton Transactions Vol -0

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

Content Provider	Royal Society of Chemistry (RSC)
Author	Wang, Jin-Yun Chen, Zhong-Ning Shi, Lin-Xi Chen, Jin-Xiang Wang, Jiang Liu, Sheng-Hua
Copyright Year	2017
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.
Starting Page	2023
Ending Page	2029
Page Count	7
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	46
Issue Number	6
Journal	Dalton Transactions
DOI	10.1039/c6dt04421b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Photochromism Ligand Cyclopentene Sodium methoxide Methanol 2-Bis(diphenylphosphino)ethane X-ray crystallography Nickel(II) chloride Nickel Photochemistry Zinc
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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

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