Synthesis of an Adaptable Molecular Barrel and Guest Mediated Stabilization of Its Metastable Higher Homologue

Banerjee, Ranit; Bhattacharyya, Soumalya; Mukherjee, Partha Sarathi

doi:10.1021/jacsau.3c00224

Cited by 6 publications

(2 citation statements)

References 84 publications

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“…Coordination-driven self-assembly has already been established as the most prominent technique for the construction of supramolecular architectures (2D and 3D) of different shapes and sizes . This self-assembly process often produces the thermodynamically most favorable product due to the kinetic reversibility present in the metal–ligand coordination . Furthermore, it comes with advantages over the bottom-up synthetic approach of a complex architecture and having similarities with natural self-assembly processes .…”

Section: Introductionmentioning

confidence: 99%

Coordination-Induced Emissive Poly-NHC-Derived Metallacage for Pesticide Detection

Maitra,

Bhattacharyya,

Purba

et al. 2024

Inorg. Chem.

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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 [Ag 4 (L) 2 ]-(PF 6 ) 4 (1) based on an aggregation-induced emissive (AIE) cored 1,1′,1″,1‴-((1,4phenylenebis(ethene-2,1,1-triyl))tetrakis(benzene-4,1-diyl))tetrakis(3-methyl-1Himidazol-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.

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Section: Introductionmentioning

confidence: 99%

Coordination-Induced Emissive Poly-NHC-Derived Metallacage for Pesticide Detection

Maitra,

Bhattacharyya,

Purba

et al. 2024

Inorg. Chem.

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“…In the past two decades, there has been a significant advancement in the discovery of various architectures through this strategy of metal–ligand coordination-driven self-assembly . Particularly, the synthesis of coordination cages has seen notable progress by strategically employing cis -blocked Pd(II) or Pt(II) complexes . These complexes have a unique configuration with two available coordination sites at an angle of 90°.…”

Section: Introductionmentioning

confidence: 99%

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

Maitra,

Bhattacharyya,

Hickey

et al. 2024

J. Am. Chem. Soc.

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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 Pd 16 L 8 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(NO 3 ) 2 ] acceptor [tmeda = N,N,N′,N′-tetramethylethane-1,2diamine] produced 1, and the geometry was determined by single-crystal X-ray diffraction study. Unlike the typically observed tri-or tetrafacial barrel, the present Pd 16 L 8 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.

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Stimuli‐Mediated Structural Interchange Between Pd₆ and Pd₁₂ Architectures: Selective Recognition of E‐Stilbene by the Pd₆ Architecture and its Photoprotection

Aggarwal,

Banerjee,

Hickey

et al. 2024

Angewandte Chemie

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The dynamic behaviour of metal‐ligand bonding cultivates stimuli‐mediated structural transformations in self‐assembled molecular architectures. The propensity of synthetically designed self‐assembled systems to interchange between higher‐order architectures is increased multi‐fold when the building blocks have higher conformational degrees of freedom. Herein, we report a new ligand, (2,7‐bis(di(pyridin‐4‐yl)amino)‐9H‐fluoren‐9‐one) (L), which, upon self‐assembly with a cis‐[(ethylene‐1,2‐diamine)Pd(NO3)2] acceptor (M), resulted in the formation of a M6L3 trifacial barrel (C1) in water. Interestingly, during crystallization, a rare M12L6 triangular orthobicupola architecture (C2) was generated along with C1. C2 could also be generated in solution via the application of several stimuli. C1 in aqueous medium could stabilize one trans‐stilbene (tS) or cis‐stilbene (cS) molecule in its cavity, with a selectivity for the former from their mixture. Moreover, C1 acted as an effective host to prevent the otherwise facile photoisomerization of tS to cS inside its hydrophobic cavity under UV irradiation. Conversely, the visible‐light‐induced reverse isomerization of encapsulated cS to encapsulated tS could be achieved readily due to the better stabilization of tS within the cavity of C1 and its transparency to visible light. A multi‐functional system was therefore designed, which at the same time is stimuli‐responsive, shows isomer selectivity, and photo‐protects trans‐stilbene.

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Synthesis of an Adaptable Molecular Barrel and Guest Mediated Stabilization of Its Metastable Higher Homologue

Cited by 6 publications

References 84 publications

Coordination-Induced Emissive Poly-NHC-Derived Metallacage for Pesticide Detection

Coordination-Induced Emissive Poly-NHC-Derived Metallacage for Pesticide Detection

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

Stimuli‐Mediated Structural Interchange Between Pd₆ and Pd₁₂ Architectures: Selective Recognition of E‐Stilbene by the Pd₆ Architecture and its Photoprotection

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Synthesis of an Adaptable Molecular Barrel and Guest Mediated Stabilization of Its Metastable Higher Homologue

Cited by 6 publications

References 84 publications

Coordination-Induced Emissive Poly-NHC-Derived Metallacage for Pesticide Detection

Coordination-Induced Emissive Poly-NHC-Derived Metallacage for Pesticide Detection

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

Stimuli‐Mediated Structural Interchange Between Pd6 and Pd12 Architectures: Selective Recognition of E‐Stilbene by the Pd6 Architecture and its Photoprotection

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

Stimuli‐Mediated Structural Interchange Between Pd₆ and Pd₁₂ Architectures: Selective Recognition of E‐Stilbene by the Pd₆ Architecture and its Photoprotection