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

Abstract

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 (Etmbt)[AgI] (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 (Etmbt) and a rare inorganic (AgI) 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.

A Novel Tetranuclear Copper(I) Iodide Metal–Organic Cluster [Cu4I4(Ligand)5] with Highly Selective Luminescence Detection of Antibiotic

“…Each EBT ligand was formed from an HBT molecule via in situ reactions. As shown in Scheme S1, the N-alkylation reaction introduces an ethyl on the thiazole N atom; meanwhile, the sulfhydryl group was deprotonated and further coordinates to the neutral [Cu 4 I 4 ] core via forming a Cu–S bond. , The Cu–I and Cu–S bond distances are in their normal ranges of 2.517(1)–2.785(1) Å and 2.234(1)–2.354(1) Å, respectively . The Cu1···Cu2′ distance of 2.684(1) Å is shorter than the sum of the van der Waals radii of Cu, suggesting there are Cu···Cu interactions in UJN-Cu .…”

Novel Three-Dimensional Semiconducting Materials Based on Hybrid d10 Transition Metal Halogenides as Visible Light-Driven Photocatalysts

“…In recent years, a large number of organic cation-directed hybrid metal halogenide materials have received a great deal of attention because of their distinctive photoelectric properties. − It is found that the template or structure-directing agent (SDA) occupies a very significant position in the crystal structure construction and band structure decorating as well as photoelectric property regulation of hybrid metal halogenide materials . These surprising discoveries incite us to explore new types of stable visible light-driven photocatalysts via the introduction of conjugated organic cations as photosensitive templates and electron acceptors into binary CuX or AgX based on the idea of electronic band structural decoration.…”

(3-Phenylpyridin-1-ium)SbI4: Coulomb Interaction-Assembled Lead-free Hybrid Perovskite-like Semiconductor

“…The (SbI 4 ) − anionic chain adopts a zigzag fashion that is formed by adjacent (SbI 6 ) octahedra each sharing two nonadjacent edges. The organic moieties in the molecular structure are mono-protonated for charge balance requirement, , which pack equimolarly with their oppositely oriented cations in the crystal lattice (Figure c). The nearest centroid-to-centroid distance between two neighboring 3ppi cations is 3.866 (1) Å, being slightly longer than 3.8 Å, which indicates there are no significant π···π packing interactions within the organic counterions.…”