RESUMO
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.
RESUMO
Developing sensitive, rapid, and convenient methods for the detection of residual toxic pesticides is immensely important to prevent irreversible damage to the human body. Luminescent metal-organic cages and macrocycles have shown great applications, and designing highly emissive supramolecular systems in dilute solution using metal-ligand coordination-driven self-assembly is demanded. In this study, we have demonstrated the development of a silver-carbene bond directed tetranuclear silver(I)-octacarbene metallacage [Ag4(L)2](PF6)4 (1) based on an aggregation-induced emissive (AIE) cored 1,1',1â³,1â´-((1,4-phenylenebis(ethene-2,1,1-triyl))tetrakis(benzene-4,1-diyl))tetrakis(3-methyl-1H-imidazol-3-ium) salt (L). A 36-fold enhanced emission was observed after metallacage (1) formation when compared with the ligand (L) in dilute solution due to the restriction of intramolecular motions imparted by metal-ligand coordination. Such an increase in fluorescence made 1 a potential candidate for the detection of a broad-spectrum pesticide, 2,6-dichloro-nitroaniline (DCN). 1 was able to detect DCN efficiently by the fluorescence quenching method with a significant detection limit (1.64 ppm). A combination of static and dynamic quenching was applicable depending on the analyte concentration. The use of silver-carbene bond directed self-assembly to exploit coordination-induced emission as an alternative to AIE in dilute solution and then apply this approach to solve health and safety concerns is noteworthy and carries a lot of potential for future developments.
RESUMO
A tetraphenylethylene (TPE)-based flexible imidazolium (L) salt was used to develop a di-nuclear silver(I)-tetracarbene (1) complex. Coordination-induced rigidity upon formation of 1 exhibited a 6-fold increase in emission intensity in acetonitrile compared to starting L. Despite TPE being a well-known aggregation-induced emissive moiety, AgI-N-heterocyclic carbene (NHC) complex 1 had a remarkably higher fluorescence emission (4-fold) in dilute solution when compared with L in its aggregated state. Finally, this enhanced emission was used to institute a new platform for an artificial light-harvesting system. 1 acted as an energy donor and efficiently transferred energy to Eosin Y (ESY) with a high saturation at a 67:1 (1/ESY) molar ratio. Use of rigidification-induced emission of the AgI-NHC complex to fabricate a light-harvesting scaffold is a new approach and can greatly impact the generation of smart materials.
