Self-Assembly of a Water-Soluble Pd16 Square Bicupola Architecture and Its Use in Aerobic Oxidation in Aqueous Medium

Maitra, PK and Bhattacharyya, S and Hickey, N and Mukherjee, PS (2024) Self-Assembly of a Water-Soluble Pd16 Square Bicupola Architecture and Its Use in Aerobic Oxidation in Aqueous Medium. In: Journal of the American Chemical Society, 416 . pp. 15301-15308.

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Abstract

Designing supramolecular architectures with uncommon geometries has always been a key goal in the field of metal-ligand coordination-driven self-assembly. It acquires added significance if functional building units are employed in constructing such architectures for fruitful applications. In this report, we address both these aspects by developing a water-soluble Pd16L8 coordination cage 1 with an unusual square orthobicupola geometry, which was used for selective aerobic oxidation of aryl sulfides. Self-assembly of a benzothiadiazole-based tetra-pyridyl donor L with a ditopic cis-(tmeda)Pd(NO3)2 acceptor tmeda = N,N,N�,N�-tetramethylethane-1,2-diamine produced 1, and the geometry was determined by single-crystal X-ray diffraction study. Unlike the typically observed tri- or tetrafacial barrel, the present Pd16L8 coordination assembly features a distinctive structural topology and is a unique example of a water-soluble molecular architecture with a square orthobicupola geometry. Efficient and selective aerobic oxidation of sulfides to sulfoxides is an important challenge as conventional oxidation generally leads to the formation of sulfoxide along with toxic sulfone. Cage 1, designed with a ligand containing a benzothiadiazole moiety, demonstrates an ability to photogenerate reactive oxygen species (ROS) in water, thus enabling it to serve as a potential photocatalyst. The cage showed excellent catalytic efficiency for highly selective conversion of alkyl and aryl sulfides to their corresponding sulfoxides, therefore without the formation of toxic sulfones and other byproducts, under visible light in aqueous medium. © 2024 American Chemical Society.

Item Type:	Journal Article
Publication:	Journal of the American Chemical Society
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society.
Keywords:	Architecture; Geometry; Ligands; Oxidation; Self assembly; Single crystals, Aerobic oxidations; Aqueous media; Aryl sulphides; Benzothiadiazoles; Building units; Coordination-driven self assembly; Ligand coordination; Metal ligands; Supramolecular architectures; Watersoluble, Sulfur compounds
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	13 Aug 2024 06:19
Last Modified:	13 Aug 2024 06:19
URI:	http://eprints.iisc.ac.in/id/eprint/85279

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