A simultaneous disulfide bond cleavage, N,S-bialkylation/N-protonation and self-assembly reaction: syntheses, structures and properties of two hybrid iodoargentates with thiazolyl-based heterocycles

Solvothermal reactions of AgI with the vulcanization accelerator 2,2'-dibenzothiazolyl disulfide and hydroiodic acid in alcohols afford two hybrid iodoargentates with one-dimensional structures, namely (Et mbt)[Ag I ] (1, Hmbt = 2-mercaptobenzothiazole) and {(Hmbt)[AgI]} (2). The syntheses of b...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2016-12, Vol.45 (47), p.19062-19071
Main Authors: Liu, Guang-Ning, Li, Ke, Fan, Qing-Shun, Sun, Hui, Li, Xin-Yu, Han, Xiao-Nan, Li, Yu, Zhang, Zhen-Wei, Li, Cuncheng
Format: Article
Language:English
Subjects:
Alcohols
Bonding
Chain reactions
Chains
Chemical bonds
Cleavage
Disulfides
Self assembly
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Summary:Solvothermal reactions of AgI with the vulcanization accelerator 2,2'-dibenzothiazolyl disulfide and hydroiodic acid in alcohols afford two hybrid iodoargentates with one-dimensional structures, namely (Et mbt)[Ag I ] (1, Hmbt = 2-mercaptobenzothiazole) and {(Hmbt)[AgI]} (2). The syntheses of both 1 and 2 involve unprecedented multiple in situ reactions. Specifically, a simultaneous disulfide bond cleavage, N and S donor atoms bialkylation, and self-assembly reaction lead to 1 that contains a discrete N,S-biethylated cation (Et mbt) and a rare inorganic (Ag I ) anionic chain, while a simultaneous disulfide bond cleavage, N-protonation and self-assembly reaction affords 2 which features zwitterionic Hmbt molecules coordinating with the opposite side Ag atoms of a neutral inorganic (AgI) chain via forming Ag-S coordination bonds. The simultaneous alkylation on a thiazolyl-N donor and a thiol-S donor atom for a thiazolyl-based heterocycle using inexpensive alcohols and haloids under solvothermal conditions instead of traditional two-step organic synthesis was found for the first time. The two compounds have band gaps of 2.95 eV for 1, and 2.78 eV for 2 exhibiting an observed blue shift compared with bulk AgI. Also, 1 and 2 can be used as effective heterogeneous photocatalysts for methyl orange dye treatment under UV light irradiation.
ISSN:1477-9226
1477-9234
DOI:10.1039/c6dt03776c